WO2007114134A1 - Resin composition containing olefin block polymer and use of the same - Google Patents

Resin composition containing olefin block polymer and use of the same Download PDF

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Publication number
WO2007114134A1
WO2007114134A1 PCT/JP2007/056573 JP2007056573W WO2007114134A1 WO 2007114134 A1 WO2007114134 A1 WO 2007114134A1 JP 2007056573 W JP2007056573 W JP 2007056573W WO 2007114134 A1 WO2007114134 A1 WO 2007114134A1
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WIPO (PCT)
Prior art keywords
polymer
olefin
block
polyolefin
layer
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PCT/JP2007/056573
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French (fr)
Japanese (ja)
Inventor
Takayuki Onogi
Hideyuki Kaneko
Tomoaki Matsugi
Koutarou Suzuki
Nobuo Kawahara
Seiji Ota
Shigeyuki Yasui
Original Assignee
Mitsui Chemicals, Inc.
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Publication date
Priority claimed from JP2006092164A external-priority patent/JP2007262325A/en
Priority claimed from JP2006151400A external-priority patent/JP2007321025A/en
Priority claimed from JP2006151401A external-priority patent/JP2007321026A/en
Priority claimed from JP2006197479A external-priority patent/JP2008024794A/en
Application filed by Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Priority to EP07740011A priority Critical patent/EP2006326A4/en
Priority to US12/225,671 priority patent/US20090136774A1/en
Publication of WO2007114134A1 publication Critical patent/WO2007114134A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer

Definitions

  • Resin composition comprising olefin-based block polymer and use thereof
  • the present invention relates to a resin composition comprising polyolefin and a polar resin. More specifically, the present invention relates to a resin composition excellent in mechanical properties such as impact resistance and tensile strength and solvent resistance.
  • the present invention also relates to an adhesive comprising the resin composition, a film or sheet, a building material 'civil engineering material, an automobile interior / exterior material or a gasoline tank, an electric' electronic component, an aqueous emulsion, a solvent dispersion, a medical treatment.
  • an adhesive comprising the resin composition, a film or sheet, a building material 'civil engineering material, an automobile interior / exterior material or a gasoline tank, an electric' electronic component, an aqueous emulsion, a solvent dispersion, a medical treatment.
  • Sanitary materials, daily goods, and laminated structures including at least one layer of the resin composition.
  • Polyolefins are excellent in processability, chemical resistance, electrical properties, mechanical properties, etc., and are therefore processed into extrusion molded products, injection molded products, hollow molded products, films, sheets, etc. Used for applications.
  • polyolefin is a non-polar resin that does not have a polar group in its molecule, it adheres to polar substances that have poor affinity with metals and various polar substances. Also, blending with polar resins was difficult.
  • Methods for improving the physical properties of polyolefin include a method of adjusting the type and molar ratio of monomers, a method of changing the arrangement of monomers such as random and block, and a method of graft copolymerizing polar monomers to polyolefin.
  • Various methods have been tried in the past.
  • a force is generally used to react the polyolefin with a radically polymerizable monomer in the presence of a radical initiator.
  • the graft copolymer obtained by such a method is used.
  • the polymer often contains a homopolymer of a radically polymerizable monomer or unreacted polyolefin, and the graft structure is not uniform.
  • the physical properties of polyolefin greatly change because of the graft polymerization and the cross-linking reaction and decomposition reaction of the polymer chain.
  • Polyolefin may be used by being laminated with other resins.
  • Polyester film is excellent in mechanical properties and chemical resistance, and by utilizing these properties, it can be used in various applications in the form of laminates with polyethylene, polypropylene, and other polyolefin resin films. It is used.
  • Polycarbonate film is excellent in transparency and impact resistance, and polymethylmethalate film is excellent in transparency, weather resistance, printability, etc. Utilizing these characteristics, lamination with various plastic films is attempted. It has been.
  • EthyleneBuluric acetate copolymer saponified film, polyvinylidene chloride film, and polyamide film are excellent in gas barrier properties, and their high gas barrier properties are used to make polyethylene, polypropylene, etc.
  • Polysalt film film is excellent in transparency, chemical resistance, printability, mechanical properties, etc., so it is useful for many industries by laminating with general-purpose plastic film.
  • styrene A modified block copolymer obtained by graft polymerization of maleic anhydride to a hydrogenated product of a styrene block copolymer or an adhesive comprising the polymer and a solvent is known (Patent Documents 2 and 3). Also disclosed is a method in which a mixture of thermoplastic polyurethane and aromatic vinyl compound “conjugated hydrogen polymer block hydrogenated product” is used as an adhesive (Patent Document 4). However, since the adhesive strength of these adhesives is not sufficient, There is a need for an adhesive that can more strongly bond a base material such as a resinous resin and a base material such as an olefin resin.
  • the production of the laminated film as described above is carried out by a method of adhering and laminating between plastic films using a solvent-type adhesive and a method of laminating using a hot melt adhesive. It is divided into two. Conventionally, when laminating polyester film, polycarbonate film, acrylic polymer film, ethylene acetate butyl copolymer saponified film, polychlorinated vinylidene film, polychlorinated butyl film, etc. with other polymer films Solvent-based adhesives have been widely used, but there are problems in terms of natural environmental pollution due to the use of organic solvents, work environment deterioration and safety, and a lamination technology that does not use solvent-based adhesives has been required. .
  • the present inventors have included a layer containing an olefin-based polymer as a main component, a polar vinyl-based plastic, an engineering plastic, a bio-derived polymer, a thermoplastic elastomer, a natural or artificial fiber, At least a layered structure that is strongly bonded via a hot-melt adhesive layer containing a specific block polymer.
  • the inventors have intensively studied to develop a laminated structure and arrived at the present invention.
  • Patent Document 1 International Publication WO98Z02472 Pamphlet
  • Patent Document 2 Japanese Patent Publication No. 4-45532
  • Patent Document 3 Japanese Patent Publication No. 63-65116
  • Patent Document 4 Japanese Patent Laid-Open No. 10-202799
  • An object of the present invention is to provide a resin composition excellent in mechanical properties such as impact resistance and tensile strength, and solvent resistance.
  • Another object of the present invention is to provide a layer containing an olefin-based polymer as a main constituent component.
  • the rosin composition (C) according to the present invention comprises:
  • a resin composition comprising an olefin-based block polymer (A2), wherein the olefin-based block polymer (A2) force is a polyolefin component, and the solubility parameter is in the range of 18 to 25 j / m.
  • Block (b) which is a polymer residue of a certain bull monomer, is a structural unit, and the block (a) and the block (b) are covalently bonded to each other! /
  • the resin composition (C) according to the present invention comprises:
  • Polycarbonate resin (bl), acrylic resin (b2), vinyl polymer (b3), and polyphenylene oxide (b4) force One or more selected resin (B) 1-98.9 wt% (However, the total amount of (Al), (A2) and (B) is 100% by weight).
  • the content of the block (b) constituting the olefin-based block polymer (A2) in the (A2) is preferably 0.1 to 70% by weight.
  • the block (b) constituting the olefin-based block polymer (A2) comprises (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, (meth) acrylamide and Its derivatives, maleic acid and its derivatives, maleimide and its derivatives, and vinyl esters. It is also preferred to consist of one or more structural units derived from the selected bull monomer.
  • Block constituting the olefin-based block polymer (A2) (b) 1S One or more butyl monomers selected from styrene, acrylonitrile, 2-hydroxyethyl methacrylate, glycidyl methacrylate and methyl methacrylate are combined with radicals (co-polymers). It is also preferred that it is a polymer residue obtained by polymerization. [0018] Furthermore, in the present invention, the block (b) constituting the olefin-based block polymer (A2)
  • the block (a) constituting the olefin-based block polymer (A2) is a crystalline polyolefin residue having a melting point of 70 ° C. or more.
  • the content of the component derived from the block (b) in the room temperature black mouth form insoluble component of the greave composition is 0.1 to 70% by weight.
  • olefin-based block polymer (A2) it is also preferred that 0.5 to 5 blocks (b) are bonded per block (a) -molecular chain.
  • a laminated structure according to the present invention comprises:
  • Polar bull plastic aromatic vinyl polymer, polyester, polyamide, polycarbonate, engineering plastic, bio-derived polymer, thermoplastic elastomer, natural or artificial fiber, and metal at least one type selected It is characterized in that it has at least a part of a structure in which a layer (L3), a force layer (L1), a Z layer (L2), and a Z layer (L3) are laminated in this order.
  • the resin composition (C) is composed of polyolefin (A1) and olefin-based block polymer (A2).
  • (Tg) is 25 ° C or less.
  • Crystallinity in which the endothermic peak due to the melting point (Tm) measured by DSC of the block (a) constituting the olefin block polymer (A2) constituting the resin composition (C) is 50 ° C or higher. Also preferred is a polyolefin residue.
  • the resin composition according to the present invention is excellent in mechanical properties such as impact resistance, tensile strength, bending strength, and solvent resistance.
  • the laminated structure according to the present invention includes a layer containing an olefin-based polymer as a main constituent component.
  • a layer consisting of at least one selected from polar-bule plastics, polyesters, polyamides, polycarbonates, engineering plastics, biological polymers, thermoplastic elastomers, natural or artificial fibers, and metal fibers. It has excellent interlayer adhesion.
  • the rosin composition (C) according to the present invention comprises:
  • a resin composition comprising an olefin-based block polymer (A2), wherein the olefin-based block polymer (A2) force is a polyolefin component, and the solubility parameter is in the range of 18 to 25 j / m.
  • the block (b), which is a polymer residue of a certain bull monomer, is used as a structural unit, and the block (a) and the block (b) are covalently bonded to each other.
  • the rosin composition (C) according to the present invention comprises:
  • Olefin block polymer (A2) is Olefin block polymer (A2)
  • the polycarbonate resin (bl), the acrylic resin (b2), the vinyl polymer (b3), and the poly (ethylene oxide) (b4) are preferably composed of one or more types of resin (B) whose forces are also selected.
  • the polyolefin (A1) used in the present invention is a (co) polymer of at least one olefin selected from a-olefin having 2 to 20 carbon atoms.
  • Examples of the ⁇ -olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2 butene, 1-pentene, 3-methyl 1-butene, 1-hexene, 4-methyl 1 —Pentene, 3-methyl 1-pentene, 1-otaten, 1-decene, 1-dodecene, 1— Linear or branched ⁇ -olefins such as tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2 methyl 1,4 , 5, 8 Dimethanol 1, 2, 3, 4, 4a, 5, 8, 8a—cyclic olefins such as octahydronaphthalene.
  • Polyolefin (A1) is a polar monomer such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene 2 , 3 ⁇ , ⁇ unsaturated carboxylic acids such as dicarboxylic acid anhydrides, and a, j8 unsaturated carboxylic acid metal salts such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, calcium salts; Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacrylic acid A, ⁇ such as ethyl, n-propyl methacrylate, iso
  • Polyolefin (A1) may be copolymerized with a small amount of butylcyclohexane, gen or polyene.
  • gen or polyene a cyclic or chain compound having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms and having two or more double bonds is used.
  • aromatic vinyl compounds such as styrene, ⁇ —methylolstyrene, m-methylstyrene, p— Such as methylol styrene, ⁇ , ⁇ dimethyl styrene, ⁇ ethyl styrene, m-ethyl
  • Mono- or polyalkyl styrene Mono- or polyalkyl styrene; functional group-containing styrene derivatives such as methoxy styrene, ethoxy styrene, bull benzoic acid, methyl bull benzoate, burbendyl acetate, hydroxy styrene, ⁇ -chlorostyrene, p-chlorostyrene, dibulubenzene;
  • Examples include 3-phenylpropylene, 4-phenylpropylene, and ⁇ -methylstyrene.
  • 16 kg is usually from 0.01 to 200 gZlO, preferably from 0.1 to LOOgZlO.
  • Such a polyolefin (A1) can be produced by a conventionally known method.
  • the polyolefin (A1) when the polyolefin (A1) has stereoregularity, it may be either syndiotactic polyolefin or lysotactic polyolefin.
  • polyethylene and polypropylene are preferably used as the polyolefin (A1).
  • Preferable polyethylene includes ethylene homopolymer, ethylene 'a-olefin copolymer and the like.
  • the ethylene 'a-olefin copolymer is, for example, a random copolymer of ethylene and at-olefin having 4 to 12 carbon atoms.
  • examples of a-olefin having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl 1-pentene, 1-octene, 1-decene, 1 —Dodecen.
  • the structural unit derived from ethylene is present in a proportion of 65 to 99% by weight, preferably 75 to 96% by weight, and an a having 4 to 12 carbon atoms.
  • constituent units derived from Orefuin is 1-35 weight 0/0, preferably desired to be present in a proportion of 4-25 wt%.
  • the ethylene / ⁇ -olefin copolymer has a melt flow rate (MFR: ASTM D12 38: 190. C, load 2.16 kg) force of 0.01 to 200 gZlO, preferably 0.05 to 50 gZlO. Is in range.
  • polypropylene for example, propylene homopolymer, propylene'ex
  • examples thereof include an olefin copolymer, a copolymer of propylene, ⁇ -olefin and a non-conjugated digen represented by the following formula (1), and a hydrogenated product of the copolymer.
  • R 3 and R 4 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 20. ]
  • the alkyl group having 1 to 6 carbon atoms of R 3 and R 4 may be linear or branched. Specifically, methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, s butyl group, t butyl group, n-pentyl group, isopentyl group, t pentyl group, neopentyl group, n —Hexyl group, isohexyl group and the like can be mentioned.
  • polypropylene when polypropylene is a copolymer, it may be a random copolymer or a block copolymer.
  • a-olefins to be copolymerized with propylene include ethylene, 1-butene, 4-methyl 1-pentene, 1-hexene, 1-octene, and the like. These ⁇ -olefins are used alone. However, two or more types may be used.
  • the method for producing polypropylene is not particularly limited, and can be produced by a well-known method using a well-known catalyst such as a Cidara 'Natta catalyst or a meta-locene catalyst.
  • a crystalline polymer can be preferably used, and in the case of a copolymer, it may be a random copolymer or a block copolymer.
  • stereoregularity and the molecular weight as long as they satisfy the moldability and have a strength that can be used when formed into a molded body.
  • Commercially available rosin can be used as it is.
  • the melting point (Tm) of polypropylene is usually 150 to 170 ° C, preferably 155 to 167 ° C.
  • the melt flow rate of polypropylene (MFR: ASTM D1238: 230.C, load 2.16 kg) is usually 0.3 to 200 gZlO min, preferably 0.4 to: LOOgZlO min, more preferred Or 0.5 to 70 g ZlO.
  • propylene homopolymers and propylene / ethylene block copolymers can be preferably used among such polypropylene resins from the viewpoints of injection molding properties and heat-resistant rigidity.
  • a propylene polymer (A1) having a propylene-derived structural unit of 50 mol% or more, preferably 80 mol% or more can be preferably used.
  • polypropylene has an isotactic pentad fraction (mmmm fraction) of a propylene homopolymer portion measured by 13 C-NMR, preferably 96.0% or more, more preferably 96.5%. As mentioned above, it is most preferable that it is 97.0% or more.
  • the isotactic pentad fraction (mmmm fraction) force of the propylene homopolymerized portion in polypropylene is less than 6.0%, and the flexural modulus and Z or heat resistance may decrease.
  • the isotactic pentad fraction (mmmm fraction) is a method described by A. Zambelli et al. In Macromolecules, Vol. 6,925 (1973), that is, a 13 C-NMR method (nuclear magnetism). This is the isotactic fraction of pentad units in a polypropylene molecular chain, measured by the gas resonance method), and the proportion of propylene monomer units in which five propylene units are consecutively isotactically bonded.
  • the polyolefin (A1) may be used in combination of two or more types.
  • a combination of crystalline polyolefin and amorphous or low crystalline polyolefin may be used. Can be mentioned.
  • the olefin-based block polymer (A2) used in the present invention has a block ( a ) which is a polyolefin component and a block (b) which is a polymer residue of a butyl monomer having a solubility parameter in the range of 18 to 25 jZm.
  • the block (a) and the block (b) have a structure connected by a covalent bond.
  • the olefin-based block polymer (A2) has a block (b) (A) —It is preferable that 0.5 to 5 bonds per molecular chain.
  • the olefin-based block polymer (A2) may have a plurality of blocks (a) and blocks (b) having different compositions and molecular weights.
  • the olefin-based block polymer (A2) has a block (a) of 20 to 99.9 parts by weight, preferably 30 to 90 parts by weight, and a block (b) of 0.1 to 70 parts by weight, preferably 10 to 10 parts by weight. Contains 70 parts by weight.
  • the performance as a compatibilizer of the olefin-based block polymer (A2) is improved, the dispersed particle size of the island phase is reduced, and the mechanical strength is increased. Will improve.
  • the olefin-based block polymer (A2) has an MFR (230 ° C, 2.16 kg load) of 0.01 to 5
  • It is preferably in the range of OgZlO minutes.
  • the block (a) is a segment derived from halogen-modified polyolefin ( a ') obtained by halogenating selected polyolefins, for example, the following group forces (al) to (a5):
  • the block (b) is a homopolymer or copolymer of one or more monomers whose radical polymerizable monomer power is also selected.
  • the block (a) constituting the olefin-based block polymer (A2) those having the same structure as the polyolefin (A1) can be used.
  • a crystalline polyolefin residue having a melting point of 70 ° C. or higher, particularly preferably 80 to 180 ° C. is preferred. When the melting point is within the above range, a resin composition having high heat resistance can be obtained.
  • the melting point (Tm) is measured, for example, as follows. About 5mg of sample is packed in a special aluminum pan, and using DSCPyrisl or DSC7 made by Perkin Elma Inc., the temperature is raised from 30 ° C to 200 ° C at 320 ° CZmin and held at 200 ° C for 5 minutes. Decrease the temperature from 200 ° C to 30 ° C at 10 ° C Zmin, hold it at 30 ° C for another 5 minutes, and then obtain it from the endothermic curve when raising the temperature at 10 ° C Zmin.
  • the olefin-based block polymer (A2) has a number average molecular weight of the block (a) in the range of 5,000 to 1,000,000, preferably 10,000 to 500,000, and the number average molecular weight of the block (b) in the range of 2,000 to 200,000. Preferable ⁇ polymer is preferred in the range of 5,000-150,000. If the molecular weight of the block ( a ) is higher than 1,000,000, the boundary between polyolefin (A1) and rosin (B) The olefin-based block polymer (A2) force is less likely to be distributed on the surface, and therefore the interface is easily peeled off and the mechanical strength is reduced. When the molecular weight is lower than 5,000, the molecular chains become less entangled between the polyolefin (A 1) resin (B) and the olefin-based block polymer (A2), and the mechanical strength decreases.
  • the block (a) constituting the olefin-based block polymer (A2) may be a segment derived from halogen-modified polyolefin obtained by halogenating polyolefin, or a polar group having a radical polymerization initiation group
  • the segment may be derived from a group-containing olefin copolymer, or may be a segment derived from a polyolefin having a group 13 element of the periodic table bonded to the terminal.
  • the block (a) force constituting the olefin-based block polymer (A2) will be described in detail for a segment derived from halogen-modified polyolefin.
  • the block (a) constituting the olefin-based block polymer (A2) is a segment derived from a polar group-containing olefin copolymer having a radical polymerization initiation group
  • an application is filed by the present applicant. The details are disclosed in the published Japanese Patent Application Laid-Open No. 2002-131620, and the technical contents are introduced in the section of “Laminate” described later in this specification.
  • a segment derived from polyolefin having a group 13 element of the periodic table bonded to the terminal is disclosed in a pamphlet of WO01Z053369 filed by the present applicant.
  • the block (a) constituting the olefin-based block polymer (A2) has the following (al) to (a5) halogen-modified products obtained by applying and / or roving polyolefin (a "), which also has a group force selected as a force It can be a segment derived from polyolefin (a,).
  • the polyolefin (a ) preferably has a number average molecular weight in the range of 5,000 to 1,000,000, more preferably 10,000 to 500,000 force! / 000.
  • Polyolefin (a ) has a molecular weight distribution (Mw / Mn) of 1.5 or more.
  • halogen-modified polyolefin (a,) obtained by halogenating the polyolefin (a,) will be described.
  • copolymer (a2) A copolymer with a monoolefin-containing compound having an aromatic ring (hereinafter also referred to as “copolymer (a2)”),
  • copolymer (a 3) A copolymer with a cyclic monoolefin compound represented by the general formula (2) (hereinafter also referred to as “copolymer (a 3)”),
  • copolymer (a4) A random copolymer with a saturated carboxylic acid or a derivative thereof (hereinafter also referred to as “copolymer (a4)”),
  • (a5) is a polyolefin obtained by modifying the polymer represented by (al) to (a4) with an unsaturated carboxylic acid or a derivative thereof (hereinafter also referred to as “modified polyolefin (a5)”).
  • n is 0 or 1
  • m is 0 or a positive integer
  • q is 0 or 1.
  • R a and R b each independently represent the following atom or hydrocarbon group, and when q is 0, each bond is bonded to form a 5-membered ring.
  • Ri to R 18 and R a and R b each independently represent an atom or group selected from the group force consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.
  • the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • a hydrocarbon group a C1-C20 alkyl group, a C1-C20 halogenoalkyl group, or a C3-C15 cycloalkyl group is mentioned each independently independently.
  • examples of the alkyl group include a methyl group and an ethyl group.
  • the alkyl halide at least one of the hydrogen atoms forming the alkyl group as described above is used.
  • examples thereof include groups in which a part is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and examples of the cycloalkyl group include a cyclohexyl group.
  • R 15 and R 16 are R 17 and R 18
  • R 15 and R 17 are R 16 and R 18
  • R 15 and R 18 are Or R 16 and R 17 may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring.
  • Specific examples of the monocyclic or polycyclic ring formed here include the following.
  • the carbon atoms assigned numbers 1 and 2 are bonded to 5 (R 16 ) or R 17 (R 18 ) in the general formula (2), respectively. Represents a carbon atom.
  • cyclic Orefin represented by the general formula (2) include, but-bicyclo [2.2.1] - 2-E down derivatives, tricyclo [4.3.0.1 2 '5] - 3- decene derivatives, tricyclo [4.3.0.1 2 '5] - 3- Undesen derivatives, tetracyclo [4.4.0.1 2' 5 .1 7 ' 1 ()] -3- dodecene derivatives, pentacyclo [7.4 .0.1 2,5 .1 9,12 .0 8,13] -3-pentadecene derivatives, pentacyclo [6.5.1.1 3,6 .0 2,7 .0 9,13] -4- penta-decene derivatives, pentacyclo [8.4.0.1 2 '3.
  • the cyclic monoolefin-containing compound represented by the general formula (2) as described above is produced by subjecting cyclopentagen and olefins having a corresponding structure to Diels' Alder reaction. Can do. These cyclic olefins may be used alone or in combination of two or more.
  • a-olefin examples include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1- Examples include linear or branched ⁇ -olefins having 2 to 20 carbon atoms such as otaten, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. .
  • ethylene, propylene, 1-butene, 1-hexene, 4-methyl 1-pentene, and 1-octene are selected, and at least one olefin can be used. preferable.
  • the (co) polymer (al) is not particularly limited as long as it is obtained by homopolymerization or copolymerization of the above-mentioned a-olefin, but low density polyethylene, medium density polyethylene, and high density polyethylene are not particularly limited.
  • Ethylene polymers such as linear low density polyethylene and ultra high molecular weight polyethylene, propylene polymers such as propylene homopolymer, propylene random copolymer and propylene block copolymer, polybutene, poly (4-methyl-1 pentene) , Poly (1 hexene), ethylene propylene copolymer, ethylene-butene copolymer, ethylene monohexene copolymer, ethylene otaten copolymer, ethylene mono (4-methyl-1-pentene) copolymer, propylene- Butene copolymer, propylene mono (4-methyl-1-pentene) copolymer, propylene monohexene Copolymers, propylene Okute down copolymers preferably.
  • constitutional unit derived from propylene 50 mol% or more preferably a propylene-based polymer is preferably 80 mol 0/0 above.
  • Examples of a-olefin include ⁇ -olefins similar to those described in the above-mentioned (co) polymer (al), and specific examples of monoolefin-containing compounds having an aromatic ring include styrene, Examples thereof include styrene compounds such as vinylolene, ⁇ -methylolstyrene, chronolestyrene, styrene sulphonic acid and its salts, and vinylpyridine.
  • the copolymer (a2) is not particularly limited as long as it is obtained by copolymerization of the above-mentioned a-olefin and a monoolefin-containing compound having an aromatic ring.
  • Examples of the a-olefin include ⁇ -olefins similar to those described in the section of the (co) polymer (al), and a structure in which a cyclic monoolefin-compound force represented by the general formula (2) is induced.
  • the unit is represented by the following general formula (3).
  • n, m, q, R 1 to R 18, and R a and R b have the same meaning as in Formula (2).
  • Examples of the a-olefin include ⁇ -olefins similar to those described in the above-mentioned (co) polymer (al), and examples of the unsaturated carboxylic acid or its derivative include unsaturated monocarboxylic acid and its Derivatives, unsaturated dicarboxylic acids and derivatives thereof, and vinyl esters, such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid halide, (meth) acrylic acid amide, Maleic acid, maleic anhydride, maleic acid ester, maleic acid halide, maleic acid amide, maleic acid imide, acetic acid butyl And aliphatic vinyl esters such as butyl butyrate.
  • vinyl esters such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid halide, (meth) acrylic acid amide, Maleic acid, maleic anhydride, maleic acid ester, maleic acid halide, maleic acid
  • the copolymer (a4) is not particularly limited as long as it is a random copolymer of the above-mentioned ⁇ -olefin and an unsaturated carboxylic acid or derivative thereof, but 50 mol of the structural unit from which the ⁇ -olefin is also derived. Those containing more than 50% are preferred.
  • examples of the unsaturated carboxylic acid or derivative thereof include maleic acid, maleic anhydride, maleic ester, maleic halide, maleic amide, maleic imide and the like.
  • examples of a method for modifying the polymer represented by (al) to (a4) with an unsaturated carboxylic acid or a derivative thereof include, for example, the presence of a radical generator such as an organic peroxide, or the presence of ultraviolet rays or radiation. Examples thereof include a method in which an unsaturated carboxylic acid or a derivative thereof is reacted with the (co) polymer represented by the above (al) to (a4).
  • (al) to (a5) force group force There are no particular restrictions on the conditions and method for producing the selected polyolefin (a ").
  • Ziegler 'Natta catalyst A method such as coordination ion polymerization using a known transition metal catalyst such as a catalyst, radical polymerization under high pressure or irradiation, etc. can be used. Or those decomposed by radicals can also be used.
  • the block (a) needs to have a monoolefin-compound compound having only one carbon-carbon double bond as described above or a mono-olefin compound compound having an aromatic ring!
  • a compound having a plurality of carbon-carbon double bonds for example, a linear gen compound such as hexagen octagen, a styrene-based gen compound such as dibylbenzene, or a cyclic diolefin such as burnorbornene or ethylidene norbornene.
  • the polyolefin to be halogenated (a ")
  • the polyolefin selected from the group forces (al) to (a5) as described above is used, and these may be used in combination of two or more.
  • Halogen-modified polyolefin (a,) can be produced by halogenating the above-described polyolefin (a,).
  • Halogen content of thus obtained halogen-modified Poriore fin (a,) is from 0.01 to 70 weight 0/0, preferably from 0.02 to 50 weight 0/0, more preferably 0. 05 ⁇ 30% by weight.
  • a halogen is selected from fluorine, chlorine, bromine or iodine, and may be a combination thereof.
  • the halogen-modified polyolefin (a ') has a structure in which at least one structural unit selected from structural unit forces represented by the following general formulas (I) to (III) is connected to the terminal of the polymer main chain: And at least one constitutional unit selected from constitutional units represented by the following general formulas (IV) to (VII) in Z or the polymer main chain.
  • X represents a halogen atom
  • R la , R lb , R 2 R 2b , R 3 , R 3b , R 3e , R 1 ⁇ 2 , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, and may represent a hydrocarbon group, an oxygen-containing group, or a nitrogen-containing group These may be the same as or different from each other.
  • Examples of the hydrogen atom and the rogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine or bromine.
  • hydrocarbon group examples include carbons such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butinole, tert-butyl, neopentyl, and n-hexyl.
  • the hydrocarbon group may have a hydrogen atom substituted with halogen.
  • the hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, black mouth Of the halogenated hydrocarbon group.
  • the hydrocarbon group may be substituted with other hydrocarbon groups, for example, aryl group-substituted alkyl groups such as benzyl and Tamyl.
  • the hydrocarbon group includes a heterocyclic compound residue, an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic acid.
  • Oxygen-containing groups such as anhydride groups, amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyanos groups, isocyanano groups, cyanate ester groups, amidino groups, diazo groups
  • the amino group may be substituted with a nitrogen-containing group such as an ammonium salt!
  • 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc.
  • aryl groups such as halogen atoms, alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, aryl groups or aryloxy groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, etc.
  • Preferred is a substituted aryl group in which 1 to 5 substituents are substituted.
  • the oxygen-containing group is a group containing 1 to 5 oxygen atoms in the group. Specifically, for example, an alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group A carbonate group, a hydroxyl group, a peroxy group, a carboxylic acid anhydride group and the like, and an alkoxy group, an aryloxy group, an acetoxy group, a carbonyl group, a hydroxyl group and the like are preferable.
  • the oxygen-containing group contains a carbon atom
  • the number of carbon atoms is preferably 1 to 30, and more preferably 1 to 20.
  • alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.
  • aryloxy groups include phenoxy, 2,6-dimethyl.
  • Phenoxy, 2,4,6-trimethylphenoxy and other strong acyl groups include formyl, acetyl, benzoyl, p-chlorobenzoyl, p-methoxybenzol and other ester groups such as acetyloxy Benzyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like are preferably exemplified.
  • the nitrogen-containing group is a group containing 1 to 5 nitrogen atoms in the group. Specifically, for example, an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group , Nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, those in which the amino group has become an ammonium salt, and the like, such as amino group, imino group, amide group, imide group, A nitro group and a cyano group are preferred.
  • the nitrogen-containing group contains a carbon atom
  • the number of carbon atoms is 1 to 30 and preferably 1 to 20.
  • the amide group includes acetamide, N-methylacetamide, N-methylbenzamide, and the like.
  • the force-containing amino group include methylamino, dimethylamino-containing dimethylamino-containing dipropylamino-containing dibutylamino, and dicyclohexylamino.
  • Alkylamino group Phenylamine-containing diphenyl Ami-filled Ditolylamin-filled dinaphthylamino, methylphenylamino, etc.
  • Preferable examples include cetylimi-containing propylimi-containing butylimi-containing leumino.
  • X represents a halogen atom
  • X represents a halogen atom
  • X represents a halogen atom.
  • X represents a halogen atom
  • X represents a halogen atom
  • X represents a halogen atom.
  • X represents a halogen atom
  • halogen-modified polyolefin (a ') two hydrogen atoms are added to the carbon-carbon double bond in the structural unit represented by the above general formulas (I) to (III) at the end of the polymer main chain.
  • the structural unit force expressed as a carbon-carbon single bond is a structure in which at least one selected structural unit is connected, and the following general formulas (IV) to (VII) in Z or the polymer main chain: At least one structural unit selected from a structural unit represented by a structure in which two hydrogen atoms are added to a carbon-carbon double bond to form a carbon-carbon single bond in the structural unit represented by May have a different structure.
  • the preferred form of such a structural unit is shown below in the structural formula.
  • X represents a halogen atom
  • the polymer main chain represents the longest part of the monomer chain structure having the largest number of repeating units derived from a-olefin and the comonomer copolymerized therewith in one polymer molecular chain, There are two terminal positions in such a polymer backbone. Therefore, two hydrogen atoms are added to the structural unit represented by the above general formulas (I) to (III) and the carbon-carbon double bond contained in the structural unit at the end of the polymer main chain to form a carbon Structural unit force expressed as a bonded structure When at least one selected structural unit is connected, the maximum number of the structural units contained in one polymer molecular chain is two.
  • the structural unit represented by the following general formulas (IV) to (VII) in the polymer main chain and the carbon-carbon double bond contained in the structural unit are attached with two hydrogen atoms to form a carbon atom.
  • Structural unit force expressed as a structure with a single carbon bond When at least one selected structural unit is inserted, there is a particular restriction on the number of structural units present per molecular chain of the polymer. There is no, but too many and polyolefin This property may not be fully developed. Therefore, two hydrogen atoms are present in the carbon-carbon double bond contained in the structural units represented by the general formulas (I) to (VII) and the structural units represented by the general formulas (I) to (VII).
  • the total number of all structural units which are the total of the structural units represented as carbon-carbon single bonds added, is preferably 0.01 to 70% by weight in terms of halogen atom content. It is more preferably 0.05 to 50% by weight. Further, several kinds of these structural units may be contained in one polymer molecular chain. Among these structural units, halogen-modified products containing structural units represented by the above general formulas (I) to ( ⁇ ) having a structure in which a carbon-carbon double bond is present and a halogen atom is added to the aryl position.
  • Polyolefin (a ') is a carbon-carbon double bond existing in a molecule that can only be used as a halogenated polyolefin for use in adhesives and coating resin as well as the conventionally known chlorinated polyethylene and chlorinated polypropylene. Functionality other than halogen can be introduced by virtue of reactivity, or it can be used as a macromonomer for producing graft polymers.
  • the halogen atom content present in the rogen-modified polyolefin (a ′) can be measured, for example, by a method such as elemental analysis or ion chromatography, and the measured value is usually expressed in units of% by weight.
  • the carbon-carbon double bond content present in the halogen-modified polyolefin (a ′) can be measured by methods such as infrared spectroscopy and nuclear magnetic resonance (NMR), and the measured value is usually Expressed in units of wt% or mol%.
  • NMR nuclear magnetic resonance
  • the halogen atom present at the aryl position of the carbon-carbon double bond can be confirmed and quantified by, for example, NMR.
  • Specific examples of the confirmation of the halogen atom present at the aryl position include, for example, a signal based on a carbon-carbon double bond in proton NMR using deuterated orthodichlorobenzene as a solvent for the brominated polypropylene obtained by the above method. Is usually observed in the range of ⁇ 4.5 to 6. Oppm, and the methylene group and methine group at the aryl position to which a bromine atom is bonded are usually observed in the range of ⁇ 3.5 to 4.5 ppm.
  • the signal position is usually S 3.0 to 3.5 ppm, so whether the bromine atom is present in the aryl position or not. Are easily identifiable.
  • the signal based on the carbon-carbon double bond it is also possible to confirm the correlation with the signals of the methylene group and methine group to which the bromine atom is bonded.
  • the molecular weight of halogen-modified polyolefin (a ′) can be measured, for example, by gel permeation chromatography (GPC).
  • the value of the number average molecular weight (Mn) thus measured and the halogen-modified polyolefin From the composition ratio (molar fraction) of each unit (unit derived from each olefin monomer, unit bonded with halogen, carbon-carbon double bond unit, etc.) contained in the polyolefin (a '), carbon
  • the content of heavy bonds can be calculated as an average value per molecular chain.
  • the average force per molecular chain of the unit to which the halogen is bonded is the number of bonds per molecular chain of the block (b) bonded to the block (a) in the olefin block polymer (A2).
  • the olefin-based block polymer (A2) has 0.5 to 5 blocks (b) bonded to the block (a) -molecular chain, preferably 0.5 to 3.5 bonded to the block (b). More preferably, 0.5 to 3 are bonded. If the number of bonds per molecular chain of the block (b) bonded to the block (a) is outside this range, the olefin-based block polymer (A2) will not easily be distributed at the interface between the polyolefin (A1) and the resin (B). Therefore, the interface is easily peeled off and the mechanical strength is lowered.
  • the halogen-modified polyolefin (a,) is produced by reacting the aforementioned polyolefin (a ,,) with a halogenating agent.
  • the halogenating agent is not particularly limited as long as it can halogenate polyolefin (a ,,) to produce halogen-modified polyolefin ( ⁇ ').
  • chlorine molecule preferably chlorine molecule, bromine molecule, N chlorosuccinimide, N bromosuccinimide, N bromocaprolatatam, N bromophthalimide, 1,3-dib-mouthed 5,5-dimethylhydantoin, N-chloroglutarimide, N Bromoglutarimide, ⁇ , ⁇ 'Dib mouth moisocyanuric acid, more preferably bromine, ⁇ ⁇ ⁇ Bromosuccinimide, ⁇ Bromocaprolatatam, ⁇ Bromophthalimide, 1,3 Dib mouth moe 5,5-dimethylhydantoin, ⁇ Bromoglutar It is a compound having a Br-Br bond such as imide, ⁇ , ⁇ '-jib mouth moisocyanuric acid.
  • the reaction between the polyolefin (a ") and the halogenating agent is preferably carried out in an inert gas atmosphere.
  • the inert gas include inert gases such as nitrogen, anoregone, and helium.
  • a solvent can be used as necessary, and any solvent can be used as long as it does not inhibit the reaction.
  • Aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, fats such as cyclohexane, methylcyclohexane and decahydronaphthalene Cyclic hydrocarbons, hydrogenated solvents, black benzene, dichlorobenzene, trichloro benzene, methylene chloride, black chloroform, tetrasalt carbon, and Chlorinated hydrocarbon solvents such as trachloroethylene and tetrachloroethane, methanol solvents, ethanol, n-propanol, isopropanol, n-butanol, sec butanol and tert butanol alcohol solvents such as acetone and methyl ethyl ketone And ketone solvents such as methyl isobutyl
  • aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane
  • alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene
  • chlorine mouth And chlorinated hydrocarbon solvents such as benzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, tetrachloroethane, etc.
  • solvents can be used alone or in combination.
  • Radical initiators include, for example, azobisisoptyl-tolyl, azobis-2,4 dimethylvaleronitrile, azobiscyclohexanecarbonyl, azobis-2-amidinopropane hydrochloride, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, or 4,4 ′ Azobis-4 Sazovaleric acid and other azo initiators, benzoyl peroxide, 2,4 dichloroperoxybenzoic acid, tert-butyl peroxide, lauroyl peroxide, acetyl acetyl peroxide, diisopropyl dicarbonate, tamenhydroperoxide, tert butyl hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, methyl
  • azo initiators or peroxide initiators are preferable, and more preferable are benzoyl peroxide, tert-butyl peroxide, lauroyl peroxide, acetyl acetate, peroxide.
  • radical initiators can be used alone or in combination of two or more.
  • polyolefin (a ) As a method of reacting polyolefin (a ") with a halogenating agent, various conventionally known methods can be employed. For example, polyolefin (a") is suspended in a solvent or dissolved. In general, a method of reacting by adding and mixing a halogenating agent and, if necessary, a radical initiator at a temperature of 80 ° C.
  • a polyolefin (a ) is brought into contact with a halogenating agent and, if necessary, a radical initiator while melting and kneading at a temperature equal to or higher than its melting point, for example, 180 to 300 ° C.
  • the halogen-modified polyolefin (a ′) is produced by the above method.
  • the number average molecular weight of the block (b) constituting the olefin-based block polymer (A2) is in the range of 2,000 to 200,000, preferably ⁇ 5,000 to 150,000.
  • the number-average molecular weight force is higher than 00,00 0 !, and the olefin-based block polymer (A 2) is less likely to be distributed at the interface between the polyolefin (A1) and the resin (B), and therefore the interface is easy to peel off.
  • the mechanical strength decreases.
  • the number average molecular weight is lower than 2,000, the molecular chains become less entangled between polyolefin (A1) resin (B) and olefin-based block polymer (A2), and the mechanical strength is lowered.
  • the block (b) is a homopolymer or copolymer of one or more monomers selected from radically polymerizable monomer forces. Specifically, as the radical polymerizable monomer,
  • butyl monomers Containing butyl monomers, maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, Maleimide monomers such as butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenolmaleimide, cyclohexylmaleimide, etc., and -tolyl group-containing vinyl monomers such as acrylonitrile and meta-tallowyl-tolyl, (Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl
  • Block (b) includes (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, (meth) acrylamide and derivatives thereof, maleic acid and derivatives thereof, maleimide and derivatives thereof, and vinyl esters.
  • styrene, talari-tolyl, 2-hydroxyethyl methacrylate, and acrylic acid n- are preferred as polymers obtained by (co) polymerizing one or two or more monomers selected.
  • a polymer obtained by (co) polymerizing one or two or more monomers selected from butyl, glycidyl methacrylate, and methyl methacrylate is more preferable.
  • the polycarbonate resin (bl) is used as the resin (B), it is obtained by (co) polymerizing one or more monomers selected from styrene, acrylonitrile, and methyl methacrylate. Particularly preferred polymers are When acrylic resin (b2) is used as the fat (B), methyl methacrylate is particularly preferred. When the bull polymer (b3) is used as the resin (B), (meth) acrylic is used. It is particularly preferred that the acid and its derivatives are not more than 50 mol%, and styrene is particularly preferred when using polyphenylene oxide (b4) as the resin (B).
  • the compositional power of the (co) polymer can also be calculated.
  • the solubility parameter 1 of block (b) is in the range of 18-25, preferably in the range of 18.2-22, more preferably in the range of 18.5-20.
  • the solubility parameter 1 of the block (b) is in the range of 18 to 24, preferably in the range of 18.5 to 24, and more preferably Is also preferably in the range of 19-24. If the value of the solubility parameter is out of this range, the compatibility between the block (b) and the resin (B) decreases, the effect as a compatibilizer decreases, and the mechanical strength decreases.
  • the solubility parameter 1 of the copolymer was calculated by inputting the composition of the block (b) into CHEOPS Ver. 4.0 manufactured by Million Zillion software, Inc.
  • the composition of the block (b) can be calculated by analyzing the room-temperature chloroform-insoluble component by 1 H-NMR.
  • the content of the component derived from the block (b) contained in the room temperature black mouth form insoluble component is 0.1 to 70% by weight, preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight. %.
  • the fact that the component derived from block (b) contained in the room-temperature chloroform-insoluble component is detected is that block (a) and block (b) are covalently bonded to each other in rosin composition (C). Indicates that they are joined.
  • the content of the component derived from the block (b) contained in the room-temperature chloroform-insoluble component is within the above range, the performance of the olefin-based block polymer (A2) as a compatibilizer is improved, and the island phase is improved.
  • the dispersed particle size of the material becomes finer and the mechanical strength is improved.
  • the room-temperature black-form insoluble component is measured as follows. 5 g of the rosin composition (C) is dissolved in 100 ml of xylene reflux. Pour the solution obtained while stirring 1 L of black mouth form with a homogenizer. The polymer precipitated and the slurry solution was allowed to stand at room temperature (15-25 ° C) for 10-15 hours, and then filtered using a G3 filter at room temperature. The product and the filtrate are separated. Filtrate becomes a black mouth form insoluble component (filtrate force S black mouth form soluble component). Perform composition analysis in the black insoluble component by 1 H-NMR, and measure the weight percentage of the component derived from the block (b) contained in the room temperature black insoluble component.
  • the olefin-based block polymer (A2) has a low content of impurities such as catalyst residue components and a good oleaginous property.
  • the transition metal content incorporated during polymerization is less than lOOppm, More preferably, the transition metal content is 50 ppm or less.
  • the average particle size is 1 to 1,0 OO / zm, and the bulk density force determined by the method specified in JIS K6891 ”SO. 10 to It is preferably in the range of 90 g / cm 3 .
  • the olefin-based block polymer (A2) can be used in any form of pellets, noda-like, and veil.
  • the olefin-based block polymer (A2) is produced, for example, by atom transfer radical polymerization of one or more monomers selected for radically polymerizable monomer power using the halogen-modified polyolefin (a,) as a macroinitiator.
  • the macroinitiator is a polymer having the ability of initiating atom transfer radical polymerization, and represents a polymer having a site that can serve as an initiation point for atom transfer radical polymerization in the molecular chain.
  • Atom transfer radical polymerization is one of living radical polymerization, and is a radical polymerizable monomer using an organic halide or a sulfonyl halide as an initiator and a metal complex having a transition metal as a central metal as a catalyst.
  • the initiator used include organic halides and halogenated sulfonyl compounds.
  • a carbon-halogen bond present at the ⁇ -position of a carbon-carbon double bond or a carbon-oxygen double bond, or a single carbon. Multiple on an atom
  • a structure in which a rosin and a rogen are added is suitable as an initiator structure.
  • halogen-modified polyolefin (a ') a carbon halogen bond existing at the ⁇ -position of the carbon-carbon double bond, or a structure in which multiple halogens are added on one carbon atom is used as an initiator structure. be able to.
  • the production method of an olefin block polymer (A2) by using halogen-modified polyolefin (a ') as a macroinitiator is basically centered on transition metals in the presence of the modified polyolefin (a').
  • a radical polymerizable monomer is atom-transferred radically polymerized using a metal complex as a catalyst.
  • the transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element of the periodic table as a central metal. Further preferred are a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cyanide cuprous, cuprous oxide, cuprous perchlorate, etc. is there.
  • 2 3 3 is also suitable as a catalyst.
  • a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator.
  • bivalent iron bistriphenylphosphine complex FeCl (PPh)
  • divalent nickel bistriphenylphosphine complex NiCl (NiCl (PPh)
  • Examples of the one or more monomers selected include the same compounds as those exemplified in the above-mentioned block (b).
  • the polymerization method is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization, and the like can be applied.
  • Solvents that can be used in radical polymerization are those that do not inhibit the reaction.
  • aromatic hydrocarbon solvents such as benzene, toluene and xylene
  • aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane Solvents
  • cycloaliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene
  • black benzene dichlorobenzene, trichloro benzene, methylene chloride, black form, carbon tetrachloride and tetrachloro
  • Chlorinated hydrocarbon solvents such as ethylene, methanol, ethanol, n- propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol alcohol solvents, acetone, methyl ethyl ketone and methyl Ketone solvents
  • aromatic hydrocarbon solvents such as benzen
  • suspension polymerization or emulsion polymerization can be performed using water as a solvent.
  • solvents may be used alone or in admixture of two or more.
  • the reaction liquid becomes a uniform phase by using these solvents, but a plurality of non-uniform phases may be used.
  • the reaction temperature may be any temperature as long as the radical polymerization reaction proceeds, and is not uniform depending on the degree of polymerization of the desired polymer, the type and amount of the radical polymerization initiator and the solvent to be used. — 100 ° C ⁇ 250 ° C. Preferably, it is ⁇ 50 ° C. to 180 ° C., more preferably 0 ° C. to 160 ° C. In some cases, the reaction can be carried out under reduced pressure, normal pressure or increased pressure.
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • the olefin-based block polymer (A2) produced by the above method is isolated by using a known method such as distillation of the solvent used in the polymerization or unreacted monomer or reprecipitation with a non-solvent. Furthermore, by treating the obtained polymer with a polar solvent such as acetonitrile or THF using a Soxhlet extraction apparatus, it is possible to remove the by-product homoradical polymer.
  • a polar solvent such as acetonitrile or THF
  • the olefin-based block polymer (A2) can be produced by uniformly dissolving the olefin-based block polymer (A2) produced by the above-described production method in an appropriate solvent.
  • olefinic block polymer (A2) by mechanical pulverization, average particle size of 1 to 1,000! ! 1 Powdery halogen-modified polyolefin ( ⁇ ') with a bulk density of 0.10 to 0.50 gZcm 3
  • a method in which the halogen-modified polyolefin ( ⁇ ′) is produced by atom transfer radical polymerization in a non-molten state.
  • the average particle size of the powdery halogen-modified polyolefin ( ⁇ ) is more preferably 1 to 500 m.
  • the olefin-based block polymer (A2) When the olefin-based block polymer (A2) is used industrially, it is preferably obtained in a benign state with a low content of impurities such as catalyst components.
  • the powder is preferably in the form of a powder having an average particle size of 1 to 1,0 OO / zm and a bulk density of 0.10-0.90 gZcm 3 .
  • the process for controlling the properties of the noda can be carried out in any process for producing the olefin-based block polymer (A2).
  • the process for producing the raw polyolefin that is, the process for polymerizing olefins.
  • a method of controlling by polymerization method or a method of controlling by crystallization method is preferably used.
  • a raw material polymer that is, a normal particle-like or pellet-like polymer is preliminarily converted into a benign powder by a crystallization operation, and the olefin-based block polymer (A2) is retained while maintaining this morphology.
  • a method for producing an olefin block polymer (A2) while maintaining this morphology, by performing a crystallization operation in the step of preparing a macroinitiator and converting it into a benign powder is preferably used.
  • the crystallization operation it is possible to control the particle diameter and bulk density by precipitating polymer particles by dissolving the polymer in a good solvent and then adding a poor solvent or lowering the temperature.
  • the factors such as polymer concentration, good solvent species, poor solvent species, stirring speed, temperature drop rate, etc. are important factors for controlling the particle size and bulk density by crystallization operation.
  • the good solvent in the crystallization operation is not particularly limited as long as it can dissolve or swell the polymer, and one or more solvents can be selected depending on the type of polymer to be dissolved. However, usually it has a high affinity for polyolefins, and an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent is preferably used as the solvent.
  • toluene, xylene, black benzene, decane or a mixed solvent thereof are particularly preferably used.
  • a polyolefin having a melting point above room temperature such as polyethylene or polypropylene
  • the polymer concentration at this time is usually in the range of 5 gZL to 500 gZL, preferably 10 gZL to 300 gZL.
  • the poor solvent in the crystallization operation is not particularly limited as long as it is a solvent capable of precipitating the polymer, and one or more solvents may be selected depending on the type of polymer to be dissolved. Is possible.
  • it is usually possible to reduce the particle size by increasing the stirring speed.
  • it is generally preferable to slow the temperature lowering rate before and after the temperature at which the polymer is precipitated.
  • the temperature lowering rate at this time is usually 5 ° CZhr to 100 ° CZhr, preferably 5 ° CZhr to 50 ° CZhr.
  • Such a method for producing an olefin-based block polymer (A2) having good properties is particularly preferably used when the melting point of the polyolefin portion is 80 ° C or higher, preferably 100 ° C or higher.
  • a polymer having a well-controlled particle property can easily remove not only the solvent but also impurities such as organic residues and catalyst residues generated in the production stage by centrifugation and filtration operations. It is possible and is industrially advantageous compared to polymers with heterogeneous particle properties.
  • the production method of the olefin-based block polymer (A2) is carried out at the start of atom transfer radical polymerization, or during the polymerization, the macroinitiator that is a powdery halogen-modified polyolefin ( ⁇ ') is in an unmolten state with an atom transfer radical. Polymerization proceeds.
  • a solvent may or may not be used. Any solvent can be used as long as it does not inhibit the reaction.
  • aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane and heptane.
  • Aliphatic hydrocarbon solvents such as cyclohexane, octane, nonane, and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methyl chloride
  • Chlorinated hydrocarbons such as len, black mouth form, tetrasalt carbon and tetrachloroethylene Solvent, methanol, ethanol, n -propanol,.
  • Alcohol solvents such as propanol, n -butanol, sec butanol and tert butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, jetyl ether, di- Examples thereof include ether solvents such as n -amyl ether, tetrahydrofuran and dioxy-sol. Water can also be used as a solvent. These solvents can be used alone or in admixture of two or more.
  • the reaction temperature may be any temperature as long as the powdery halogen-modified polyolefin ( ⁇ '), which is a macroinitiator, does not melt or swell, and the radical polymerization reaction proceeds. Although it is not uniform depending on the degree of polymerization, the type of radical polymerization initiator used, and the solvent, it is usually 100 ° C to 250 ° C. Preferably, it is ⁇ 50 ° C. to 120 ° C., more preferably 0 ° C. to 100 ° C. In some cases, the reaction can be carried out under reduced pressure, normal pressure, or increased pressure.
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • the powdery olefin-based block polymer (A2) can be produced as follows.
  • a nitrogen-substituted glass reactor is charged with a powdery halogen-modified polyolefin (A,) containing a halogen atom, an organic solvent such as toluene, and a radical-polymerizable monomer such as methyl methacrylate. And heat and stir to 80 ° C to disperse the polymer in a slurry.
  • PMDETA copper bromide and N, N, N ', N ", N" -pentamethyljetylene triamine
  • Methanol is added to the reaction solution, the polymer is filtered and washed, and the precipitated polymer is dried under reduced pressure to obtain a powdery olefin-based block polymer (A2).
  • the powdery olefin-based block polymer (A2) produced by the above method has a simple filtration / washing of the catalyst residue, solvent and unreacted monomer used for polymerization! The soot can be removed by centrifugation.
  • the polycarbonate resin (bl) used in the present invention is a conventionally known polycarbonate capable of obtaining power with a divalent phenol such as bisphenol A and a carbonic acid diester or phosgene.
  • Divalent phenol includes 2,2-bis (4-hydroxyphenol) propane [bisphenol A], 1,1-bis (4-hydroxyphenol) methane, 1,1 —Bis (hydroxyl) alkanes such as bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenol) butane, 1,1-bis (4-hydroxyphenol) Examples thereof include bis (hydroxyl) cycloalkanes such as cyclohexane, dihydroxyl ethers such as 4,4′-dihydroxydiphenyl ether, and dihydroxydiarylsulfides.
  • divalent phenols Two or more kinds of these divalent phenols may be used if necessary.
  • bisphenol 8 or bisphenol A is the main component, and a small amount of other divalent phenols is contained. Is used.
  • Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, bis (diphenyl) carbonate, and jetinore carbonate. Of these, diphenyl carbonate is preferably used.
  • the polycarbonate may be treated with an end-capping agent such as an aryloxy compound or a monocarboxy compound if necessary.
  • acrylic resin (b2) used in the present invention examples include an acrylic ester polymer (polyacrylate), a methacrylic ester polymer (polymetatalylate), and a copolymer resin thereof.
  • polymetatalate examples include polymethyl metatalylate, polyethyl methacrylate, polybutinoremethalate, polylaurinoremethalate, polystearinolemetalate, Examples thereof include lysobutynole methacrylate, poly n-hexino methacrylate, poly n-octino methacrylate.
  • the acrylic resin (b2) as described above can be used alone or in combination of two or more.
  • the molecular weight of the acrylic resin (b2) is preferably in the range of 500 to 10,000 as the number average molecular weight, and more preferably in the range of 1,000 to 5,000.
  • the number average molecular weight is obtained using GPC and polystyrene as a standard.
  • Such an acrylic resin (b2) can be produced by a known polymerization method such as a solution polymerization method, a suspension polymerization method, or a bulk polymerization method.
  • the bull polymer (b3) used in the present invention is a polymer obtained from a bull monomer comprising at least one selected from an aromatic vinyl compound (ml) and a vinyl cyanide compound (m2).
  • Examples of the aromatic bur compound (ml) include styrene, butyltoluene, a -methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof.
  • Examples of the cyanide bur compound (m2) include acrylonitrile and meta-tallow-tolyl.
  • the genes include butadiene, isoprene, 4-methyl-1,3 pentagen, 1,3 pentagen, 1,4 pentagen, 1,5 hexagen, 1,4 one hexagen, 1,3 hexagen, 1, Examples include 3-aged Tatageng, 1,4-Octagen, 1,5-Old Tajtagen, 1,6 Otaj Tage, and 1,7-Octagen.
  • Examples of the vinyl polymer (b3) include a homopolymer of an aromatic vinyl compound (ml) (eg, polystyrene), and a copolymer of an aromatic vinyl compound (ml) and gen (eg, butadiene / styrene copolymer).
  • Polymer a copolymer of aromatic vinyl compound (ml) and vinyl cyanide compound (m2) (for example, acrylonitrile 'styrene copolymer, etc.), aromatic vinyl compound (m 1) and vinyl cyanide compound ( and a copolymer of m2) and gen (for example, acrylonitrile / butadiene / styrene copolymer).
  • the bull polymer (b3) used in the present invention can be produced by a conventionally known method, and a commercially available product can be used as the vinyl polymer (b3).
  • polyphenylene oxide (b4) used in the present invention examples include poly (2,6 dimethyl 1,4 phenylene) ether, poly (2 methyl 6 ethyl 1,4 phenylene) ether, poly (2 , 6 Jetyl 1,4 Phenylene) ether, Poly (2 Ethyl 6—n Propinole-1,4-Phenylene) etherole, Poly (2,6 Di n-propyl-1,4-Phenylene) ether , Poly (2-methyl-6-n-butyl-1,4 phenylene) ether, poly (2-ethyl-6 isopropyl-1,4-phenylene) ether, poly (2-methyl-6 chloro 1,4 For example, phenyl) ether, poly (2-methyl-6-hydroxyethyl-1,4phenylene) ether, poly (2-methyl-6-chloroethylenol-1,4-phenylene) etherole. Moreover, modified polyphenylene oxide obtained by modifying these polyphenyl
  • additives can be blended in the resin composition (C) of the present invention in accordance with the application within a range that does not significantly impair its purpose and effect.
  • additives that can be used include modified dispersants, lubricants, plasticizers, flame retardants, antioxidants, antistatic agents, light stabilizers, ultraviolet absorbers, and crystallization accelerators (nucleating agents).
  • Quality additives colorants such as pigments and dyes, carbon black, titanium oxide, and the like.
  • particulate fillers such as talc, clay, strength, silicates and carbonates, fibrous fillers such as glass fiber and wollastonite, and whiskers such as potassium titanate can also be blended.
  • the composition ratio of the polyolefin (A1), the olefin-based block polymer (A2), and the resin (B) constituting the resin composition (C) of the present invention is 100% by weight when the sum of the three is 100% by weight.
  • the component (A1) is usually 1 to 98.9% by weight, preferably 5 to 90% by weight.
  • the component (A2) is usually 0.1 to 50% by weight, preferably 0.5 to 30% by weight.
  • the component (A2) is less than 0.1% by weight, the effect as a compatibilizer will be reduced, and if it is more than 50% by weight, the mechanical properties will be reduced.
  • the component (B) is usually 1 to 98.9% by weight, preferably 9.5 to 95.5% by weight. If the component (B) is less than 1% by mass, the mechanical properties are degraded, and if it is greater than 98.9% by weight, the solvent resistance is degraded.
  • the resin may be included as long as the physical properties of the resin composition are not deteriorated.
  • the resin composition (C) according to the present invention has a content of a polymer of a bull monomer having a solubility parameter in a room-temperature chloroform-insoluble component in the range of 18 to 25 j / m. -50% by weight, preferably 0.3-30% by weight, more preferably 0.5-20% by weight.
  • the solubility parameter in the room-temperature chloroform-insoluble component is 18 to The weight (C) of the polymer of butyl monomer in the range of 25j / m and room temperature black mouth form soluble component
  • a polymer of bulle monomer having a solubility parameter in the room-temperature chloroform-insoluble component of the rosin composition (C) in the range of 18 to 25 JZm can be converted into an olefin-based block polymer (A2).
  • the monomer polymer is a polymer of bulle monomers that are present alone (not bound to the polyolefin component) in the composition. Therefore, the value of (C / C)
  • the weight (C) of the polymer of the bull monomer whose solubility parameter in the room temperature black mouth form insoluble component of the composition is in the range of 18 to 25 jZm, and the room temperature black mouth form of the composition
  • the weight (C) of the vinyl monomer polymer having a solubility parameter in the soluble component in the range of 18 to 25 jZm is determined as follows.
  • the preparation method of the resin composition (C) of the present invention is not particularly limited and can be adjusted by a known method such as a melting method or a solution method, and practically a melt-kneading method. Is preferred.
  • a kneading method generally used for thermoplastic resin can be applied as it is.
  • powdery or granular components, and optional components if necessary are uniformly dry mixed with a Henschel mixer, ribbon blender, V-type blender, etc., and then uniaxial or multiaxial kneading extrusion Melting and kneading can be performed with a machine, a kneading roll, a batch kneader, a kneader, a vannolly mixer or the like.
  • the melt kneading temperature of each component is not particularly limited as long as each component is melted, but is usually 160 to 350 ° C, preferably 200 to 300 ° C. .
  • the kneading order and method of each component are not particularly limited. It is also possible to remove unreacted components and decomposition products in the polymer by kneading under reduced pressure.
  • the resin composition according to the present invention can be used in various applications, for example, in the following applications.
  • the film and sheet made of the resin composition according to the present invention are excellent in any one of flexibility, transparency, adhesiveness, antifogging property, heat resistance and separability.
  • floor materials for example, floor materials, floor tiles, floor sheets, sound insulation sheets, heat insulation panels, vibration proof materials, decorative sheets, Base materials such as baseboards, asphalt modifiers, gaskets 'sealing materials, roofing sheets, waterproof sheets, etc.'
  • the automotive interior / exterior material and gasoline tank comprising the resin composition according to the present invention are excellent in rigidity, impact resistance, oil resistance and heat resistance.
  • Office electrical product parts Office computer-related parts, telephone-related parts, accesssiri-related parts, copier-related parts, electromagnetic shielding materials, speaker cone materials, speaker vibration elements, etc.
  • the aqueous emulsion containing the resin composition according to the present invention can be an adhesive for polyolefin having excellent heat sealing properties.
  • the solvent dispersion containing the rosin composition according to the present invention is excellent in dispersion stability with respect to the solvent, and exhibits good adhesion when adhering a metal or polar resin and polyolefin.
  • Laminated structure comprising at least one layer comprising the resin composition according to the present invention.
  • drug packaging material for example, drug packaging material, clothing packaging material, wallpaper, decorative board, electrical insulating film, adhesive film and tape.
  • Separation membranes such as base materials, marking films, laminates of metal plates and other materials, agricultural films, wrapping films, shrink films, protective films, plasma component separation membranes, water permselective vaporization membranes, Selective separation membranes such as ion exchange membranes, battery separators, and optical separation membranes.
  • the laminated structure according to the present invention includes a layer (Ll) containing an olefin-based polymer as a main constituent,
  • Polar bull plastic aromatic vinyl polymer, polyester, polyamide, polycarbonate, engineering plastic, biological polymer, thermoplastic elastomer 1.
  • a preferred embodiment of the present invention is an olefin-based polymer having a layer (L1) containing an olefin-based polymer as a main component, a polyolefin segment [S], and an extreme polymer segment [S].
  • Layer (L2) containing block polymer (A2), polar vinyl plastic, polyester, polyamide, polycarbonate, engineering plastic, bio-derived polymer, thermoplastic elastomer, natural or artificial fiber, and metal This is a laminated structure in which at least a part of the layer (L3), the force layer (LI), the Z layer (L2), and the Z layer (L3) are laminated in this order.
  • the components constituting the layer (L1), the layer (L2), and the layer (L3) are described in detail below in this order, and then the layer (L1), the Z layer (L2), and the Z layer (L3) are stacked in this order.
  • a laminated structure having at least a part of the structure will be described.
  • the layer (L1) is a layer containing an olefin polymer as a main constituent component.
  • “major” means that the weight proportion of the whole is 70% by weight.
  • the olefin-based polymer used in the laminated structure according to the present invention is a (co) polymerization using at least one olefin selected from ethylene and ⁇ -olefin having 3 to 20 carbon atoms. It is a polymer obtained by doing.
  • the a-olefin having 3 to 20 carbon atoms may be linear or branched, for example, propylene, 1-butene, 2-butene, 1 pentene, 3-methyl-1-butene, 1-hexene.
  • polyethylene homopropylene, poly (4-methyl 1-pentene), homopolyolefins such as poly (1 hexene), block polypropylene such as ethylene'propylene block copolymer, ethylene'propylene copolymer, Examples thereof include olefin copolymers such as ethylene'-butene copolymer, ethylene-propylene-butene copolymer, and compositions that have at least two of these.
  • the olefinic polymer has stereoregularity. When it has, it may be either syndiotactic polyolefin or isotactic polyolefin.
  • the layer (L1) if necessary, is a known additive usually added to the olefin polymer, for example, inorganic fillers such as talc, silica, my strength, clay, glass fiber, dyes and pigments, Antioxidants, processing stabilizers, weathering agents, heat stabilizers, light stabilizers, nucleating agents, lubricants, mold release agents, flame retardants, antistatic agents, coloring agents, ultraviolet absorbers, and the like can be contained.
  • the layer (L2) is a polymer layer that functions as an adhesive layer for bonding the layer (L1) and the layer (L3).
  • the layer (L2) is a layer comprising an olefin-based block polymer (A2) comprising a block (a) and a block (b), preferably a polyolefin (A1) and an olefin-based block polymer (A2).
  • a layer made of the resin composition (C) composed of polyolefin (A1) and an olefin-based block polymer (A2). is there.
  • the olefin-based block polymer (A2) preferably used in the laminated structure according to the present invention comprises a block ( a ) (polyolefin segment [S]) and a block (b) (extra-polymer segment [
  • the olefin block polymer (A2) is a skeleton represented by the following image formula (i).
  • Olefin-based block polymer (A2) consists of carbon atoms in [S] and [S]
  • the olefin block polymer (A2) and the olefin block polymer (A2) are mainly composed of
  • Q represents a hetero atom or a linking group containing a hetero atom.
  • the segment should have a chemical structural formula in which halogen radicals are removed from halogen-modified polyolefin [S '] obtained by norogenating polyolefin.
  • Halogen-modified polyolefin [S,] usually has a molecular weight distribution (MwZMn) of 1
  • Polyolefin [S "] is a repeating unit derived from polyolefin having 2 to 20 carbon atoms.
  • the polyolefin is a homopolymer or random copolymer of olefin selected from 2 to 20 carbon atoms.
  • this polyolefin may be either a isotactic polyolefin or a syndiotactic polyolefin.
  • olefins having 2 to 20 carbon atoms include linear or branched OC-olefins, cyclic olefins, and aromatic vinyl compounds.
  • linear a-olefin examples include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1- Examples thereof include dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms.
  • branched ⁇ -olefin examples include, for example, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4 Examples thereof include 4 to 20 carbon atoms, preferably 5 to 10 carbon atoms such as -methyl-1-1 hexene, 4,4 dimethyl-1-1 hexene, 4-ethyl-1-1 hexene, 3-ethyl-1-1 hexene.
  • Cyclic olefins include cyclopentene, cycloheptene, norbornene, and 5-methyl.
  • Examples thereof include 2-norbornene, tetracyclododecene, burcyclohexane and the like having a carbon atom number of ⁇ 20, preferably 3-10.
  • the GPC molecular weight profile of polyolefin [S "] is essentially a polyolefin segment
  • weight average molecular weight (Mw) is usually 1,00
  • the quantity distribution (MwZMn) is from 1 to 10, preferably from 1.5 to 8, more preferably from 1.6 to 7, even more preferably from 1.7 to 6, particularly preferably from 1.8 to 5.
  • the polyolefin segment [S] contains at least 1 —olefin having 3 or more carbon atoms.
  • a seed-containing homopolymer or copolymer, or a copolymer of ethylene and cyclic olefin is preferred. Furthermore, it is particularly preferable to exhibit isotacticity with high stereoregularity, more preferably the stereoregularity due to the ⁇ -olefin component having 3 or more carbon atoms.
  • the polyolefin segment [S] is measured by DSC.
  • the crystalline polyolefin having such properties is polyethylene or a polyolefin exhibiting high stereoregularity.
  • the copolymerization amount of the a-olefin component having 3 or more carbon atoms is preferably 0 to: LOmol%, more preferably 0 to 7 mol%.
  • highly stereoregular propylene polymers having a copolymerization amount of oc 1-year-old refin having 4 or more carbon atoms from 0 to: LOmol% are preferred. More preferred is a highly stereoregular propylene homopolymer, preferably a highly stereoregular propylene polymer having a copolymerization amount of olefins of 0 to 7 mol%.
  • olefin polymerization catalysts include TiCl-based catalysts, MgCl-supported TiCl-based catalysts, chromium-based catalysts, meta-octane-based catalysts, and bosses.
  • MgCl-supported TiCl catalysts or metallocene catalysts To metallocene catalysts, MgCl-supported TiCl catalysts or metallocene catalysts, MgCl-supported TiCl catalysts or metallocene catalysts
  • the halogen-modified polyolefin [S '] is a known halogenated polyolefin [S "].
  • halogenation method can be produced by a halogenation method using an oxidizing agent.
  • the halogenating agent include the compounds exemplified in the method for producing the halogen-modified polyolefin (a ′).
  • a peracid is used as necessary to accelerate the reaction.
  • the halogen content of the halogen-modified polyolefin [S ′] thus obtained is usually 0.01 to 70% by weight, preferably
  • halogen-modified polyolefin [S ′] is, for example, elemental analysis or ion
  • the carbon-carbon double bond content present in the halogen-modified polyolefin [S ′] is, for example, determined by infrared spectroscopy or nuclear magnetic field.
  • the halogen atom present at the aryl position of the carbon-carbon double bond can be confirmed and quantified by, for example, NMR.
  • Specific examples of the confirmation of the halogen atom present at the aryl position include, for example, protons using deuterated orthodichlorobenzene of brominated polypropylene as a solvent.
  • a signal based on a carbon-carbon double bond is usually observed in the range of ⁇ 4.5 to 6.
  • Oppm and a methylene group and a methine group at the aryl position to which a bromine atom is bonded are usually ⁇ 3.5 to 4.5 ppm.
  • the signal position when a bromine atom is introduced into a methylene group and a methine group other than the aryl position is usually ⁇ 3.0 to 3.5 ppm, so it is easy to determine whether the bromine atom is present at the aryl position or not. Can be identified. Power!
  • the polar polymer segment [S] can be introduced by using the structure as an initiator structure and polymerizing a hetero-element-containing polymerizable monomer. Viewpoint of fluidity and adhesive performance
  • the average number of introduced halogen atoms is preferably 0.3 to 10, more preferably 0.5 to 8, and even more preferably 0.7 to 5.
  • the average number N of halogens introduced per polymer chain was determined as follows.
  • the number average molecular weight obtained from GPC is Mn
  • the average molecular weight of the introduced monomer is Fw (ave)
  • the molar content of the halogen group with respect to all monomer chain units is n (mol%).
  • the average number N of halogens introduced per polymer chain (the Z chain) can be obtained from the following equation.
  • N n X Mn / [Fw (ave) X 100]
  • Specific examples of the radically polymerizable monomer used in the present invention include those similar to the radically polymerizable monomer exemplified in the description of the above-described block (b). These organic compounds may be used alone or in combination of two or more.
  • the polar polymer segment [S] includes (meth) acrylic acid and its derivatives, (meth)
  • the polar polymer in the olefin-based block polymer (A2) is used.
  • the remer segment [S] improves the adhesion between the layers (L1) and (L2) and improves the plasticizer retention.
  • the solubility parameter is in the range of 18 to 25 (jZm), because of good solubility or dispersibility in components other than the olefin-based block polymer (A2) in the layer (L2), Preferably it is in the range of 18-24 (jZm), more preferably in the range of 18.2-22 (jZm), and even more preferably in the range of 18.4-20 (JZm). It is preferably a polymer of a functional monomer.
  • the solubility parameter of the polar polymer segment [S] is the polar polymer segment [S]
  • the solubility parameter 1 is the CHEOPS manufactured by Million Zillion Software, Inc.
  • the composition of the polar polymer segment [S] can be calculated by analyzing the room-temperature chloroform-insoluble component by 1 H-NMR.
  • the polymer segment [S] in the olefin block polymer (A2) is isocyanate
  • the glass transition temperature (Tg) measured with a differential scanning calorimeter (DSC) is preferably 25 ° C. or less, more preferably 60 to 25 ° C., and even more preferably 50 to 20 ° C.
  • Radical polymerizable monomers containing a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2.2.1] Hepto-2-ene-1,6 dicarboxylic acid and the like, and examples of the derivative of the carboxyl group-containing radical polymerizable monomer include these acid anhydrides and acid anhydrides, amides, imides thereof. And derivatives such as esters.
  • radical polymerizable monomer containing a hydroxyl group examples include hydroxyethyl (meth) acrylate, 2 hydroxypropyl (meth) acrylate, 3 hydroxypropyl (meth) acrylate, 2 hydroxy 1-3 phenoxy.
  • the radical polymerizable monomer containing at least one kind of group selected from oxazoline group, maleimide group, amine group, imine group power for example, amino group-containing ethylene having ethylenic double bond and amino group
  • amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, ( Alkyl ester derivatives of acrylic acid or methacrylic acid such as meth) acryloyl acrylate, phenolaminoethyl methacrylate, cyclohexylaminoethyl methacrylate; and buramine derivatives such as N-vinyljetylamine and N-acetylbutylamine.
  • a radical polymerizable monomer containing an epoxy group is a monomer having at least one unsaturated bond and epoxy group polymerizable in one molecule.
  • Such an epoxy group-containing radical polymerizable monomer include glycidyl atylate, glycidyl metatalylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, and mono and di of tetrahydrophthalic acid.
  • Glycidyl esters mono- and glycidyl esters of itaconic acid, mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidino-reestenoles of citraconic acid, endo-cis-bicyclo [2.2.1] hept-5-one 2,3 dica Mono and rubonic acid (Nadic Acid TM) Diglycidyl esters, endo-cis bicyclo [2.2.1] hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid TM) mono and diglycidyl esters, allylic succinic acid mono and glycidyl mono And alkyl glycidyl ester (in the case of monoglycidyl ester, the alkyl group has 1 to 12 carbon atoms), ⁇ -alkyl glycidyl ester of styrene carboxylic acid, allyl glycidyl este
  • the olefin-based block polymer ( ⁇ 2) is made up of the above halogen-modified polyolefin [S '].
  • the radical copolymerization method is not particularly limited, but usually the atom transfer radical copolymerization method is preferably used.
  • the macroinitiator of the present invention is a polymer having the ability of initiating atom transfer radical polymerization, and represents a polymer having a site that can be the starting point of atom transfer radical polymerization in the molecular chain.
  • Atom transfer radical polymerization in the present invention is one of living radical polymerizations, in which a metal complex having an organic halide or halogenated sulfone compound as an initiator and a transition metal as a central metal is used.
  • This is a method of radical polymerization of a radical polymerizable monomer as a catalyst.
  • Initiators used include, for example, organic halides and halogenated sulfo-ruly compounds, especially carbon-carbon double bonds or carbon-oxygen double bonds.
  • a structure in which a carbon-halogen bond at the ⁇ -position or a plurality of halogen atoms are added on one carbon atom is suitable as the initiator structure.
  • a carbon-halogen bond present at the ⁇ -position of a carbon-carbon double bond, or a structure in which a plurality of halogens are added on one carbon atom can be used as an initiator structure.
  • the production method of ( ⁇ 2) is basically the transition metal in the presence of the modified polyolefin [S ′].
  • a radically polymerizable monomer is atom-transferred radically polymerized using a metal complex having a central metal as a polymerization catalyst.
  • the transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element of the periodic table as a central metal. Further preferred are a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cyanide cuprous, cuprous oxide, cuprous perchlorate, etc. is there.
  • 2 3 3 is also suitable as a catalyst.
  • a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator.
  • divalent iron bistriphenylphosphine Fin complexes FeCl (PPh)
  • divalent nickel bistriphenylphosphine complexes NiCl (Pb)
  • the atom transfer radical polymerization method is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization, and the like can be applied.
  • the solvent that can be used in radical polymerization any solvent that does not inhibit the reaction can be used.
  • aromatic hydrocarbon solvents such as benzene, toluene, and xylene, pentane, Aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, black benzene, dichlorobenzene, trichlorolip Chlorinated hydrocarbon solvents such as benzene, chloride methylene, chloroform, tetrasalt carbon and tetrachloroethylene, methanol, ethanol, n -propanol.
  • aromatic hydrocarbon solvents such as benzene, toluene, and xylene
  • pentane Aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane and decane
  • alicyclic hydrocarbon solvents
  • Alcohol solvents such as monopropanol, n -butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, And ether solvents such as tilether, di-n-amyl ether, tetrahydrofuran and dioxy-sol.
  • suspension polymerization or emulsion polymerization can be performed using water as a solvent. These solvents may be used alone or in combination of two or more.
  • the reaction liquid becomes a homogeneous phase by using these solvents, but it may be a heterogeneous plural phase.
  • the reaction temperature may be any temperature as long as the radical polymerization reaction proceeds, and is not uniform depending on the desired degree of polymerization of the polymer, the type and amount of the radical polymerization initiator and solvent to be used. — 100 ° C ⁇ 250 ° C. Preferably, it is ⁇ 50 ° C. to 180 ° C., more preferably 0 ° C. to 160 ° C. In some cases, the reaction can be carried out under reduced pressure, normal pressure or increased pressure.
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • the olefin-based block polymer (A2) produced by the above method is used for the solution used in the polymerization.
  • a representative method for producing the polymer (A2) has been filed by the present applicant and has already been published.
  • olefin block polymer (A2) is represented by the following general formula [C-1].
  • R 1 in the general formula [C-1] represents a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms
  • the general formula [C 2] and the general formula R 2 in the formula [C 3] represents a linear or branched aliphatic or aromatic hydrocarbon group having 1 to 18 carbon atoms
  • F 1 in the general formula [C-3] is a heteroatom.
  • F 2 in the general formulas [C 2] and [C 3] represents a group containing an unsaturated group
  • Z represents a polymer segment obtained by radical polymerization
  • W represents an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxylic acid group, a carboxylic acid ester group, an acid anhydride group, an amino group, an epoxy group, a siloxy group, and a mercapto group
  • n is an integer of 1 to 3
  • M is 0, 1 or 2
  • Z may be the same or different m W can be the same or different from each other W is the same or different atom in R 1 It may be bonded with a ring structure.
  • the olefin-based block polymer (A2) is composed of only the force [C-2].
  • the range is 1,000 to 1,000,000 and 1,000 to 500,0 respectively.
  • the range is 00.
  • Lock (a) A resin composition having excellent fluidity and adhesive performance when it is usually 0.5 to 5, preferably 0.5 to 3, more preferably 0.7 to 2 per molecular chain Is provided.
  • the olefin-based block polymer (A2) preferably the olefin-based block polymer (A 2) and Z or olefin-based block polymer (A2) are used in the layer (L2),
  • 5% is particularly preferred. If the ratio of the polar polymer segment [S2] is within this range, the solubility in the olefin-based block polymer (A2) in the layer (L2) is increased and the solubility in the layer (L3) is high. Adhesive strength between layer (L2) and layer (L3) is increased.
  • the layer (L2) constituting the laminated structure of the present invention comprises the olefin-based block polymer (A2), preferably the olefin-based block polymer (A2) and
  • olefin block polymer (A2) olefin block polymer (A2)
  • the polyolefin segment [S] is the same as the polyolefin segment [S].
  • homogeneous means a carbon atom or polar polymer bonded to the polar polymer segment [S] in the polyolefin segment [S]. In one segment [s], the carbon atom bonded to the polyolefin segment [s] is hydrogen.
  • each of the polyolefins or chemicals having a chemical structure substituted with atoms is defined as a polar polymer.
  • the polyolefin [R] has a chemical structure in which the carbon atom bonded to the polar polymer segment [S] is replaced with a hydrogen atom.
  • Polyolefins with different molecular weights and different ⁇ -olefin introduction rates are also subject to [R] as well as rioolefin, and the olefin polymers exemplified as the olefin polymers constituting the layer (L1) described above are also subject to [R]. It can be used without restriction.
  • the carbon atom bonded to the polyolefin segment [S] is replaced with a hydrogen atom.
  • the weight ratio of 2) is usually 1 to: LOO wt%, preferably 1 to 50 wt%, more preferably 1 to 30 wt%.
  • the layer (L2) contains an olefin block polymer ( ⁇ 2) and the polar polymer [Q].
  • the layer (L2) according to the present invention does not exclude any coexistence of components other than (A2), [Q] and [R].
  • a resin additive other than (A2), [Q] and [R] may be added as long as the object of the present invention is not impaired.
  • the total amount of [R] is 1 to: LOO wt% of the layer (L2), preferably 50 to: LOO wt%, and more preferably 70 to: LOO wt%.
  • Additive components added to the layer (L2) include talc, silica, My strength, clay, glass fiber, and other inorganic fillers, dyes, antioxidants, processing stabilizers, weathering agents, and heat stabilizers. Agents, light stabilizers, nucleating agents, lubricants, mold release agents, flame retardants, antistatic agents, coloring agents, ultraviolet absorbers and the like.
  • a conventionally known method can be adopted as a method for producing the resin composition constituting the layer (L2).
  • a method in which each component is mixed in a batch or sequentially with a Henschel mixer, V blender, ribbon blender, tumbler blender, etc., or a mixture obtained by such a method is further mixed with a single screw extruder. After melt-kneading with a twin-screw extruder, kneader, Banbury mixer, etc., a granulated soot can be obtained by pulverizing the obtained lumps.
  • the layer (L3) is at least selected from polar vinyl plastics, aromatic vinyl polymers, polyesters, polyamides, polycarbonates, engineering plastics, biological polymers, thermoplastic elastomers, natural or artificial fibers, and metals. But it is a layer selected from one kind. In the present invention, in the case where the layer (L3) is composed of a polar bull-type plastic or an aromatic bull-type polymer, excellent adhesion performance between the layer (L2) and the layer (L2) is exhibited.
  • polar bull plastic used in the layer (L3) include acrylic polymers, vinyl chloride polymers, vinylidene chloride polymers, ethylene vinyl acetate copolymer oxides, and the like. can do.
  • the aromatic bull polymer used in the layer (L3) is a polymer obtained by polymerizing a monomer containing an aromatic bull monomer as a component.
  • aromatic vinyl monomers include styrene, a-methylol styrene, and p-methyl styrene.
  • aromatic vinyl polymers include not only aromatic butyl homopolymers, but also various rubber polymers such as butadiene rubber, styrene butadiene copolymer, ethylene propylene copolymer, and ethylene propylene copolymer.
  • Aromatic vinyl polymer styrene maleic anhydride copolymer, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile butadiene copolymer, styrene-acrylonitrile acrylate copolymer, etc. It can be illustrated.
  • the polyester used in the layer (L3) is not particularly limited as long as it has an ester bond in the polymer main chain and can be melted by heating.
  • Examples of the polyester that can be used in the present invention include a polyester obtained by a reaction of a dicarboxylic acid component and a diol component. Examples include polyesters obtained by ring-opening polymerization of reesters and latatones (polylatatanes), polyesters obtained by polycondensation of hydroxycarboxylic acid or its ester-forming derivatives, and one or two of these polyesters. The above can be used. Among them, in the present invention, a polyester that is substantially formed from a dicarboxylic acid component and a diol component is preferably used.
  • examples include cycloaliphatic diols such as sandimethanol and cyclohexanediol; diols derived from polyalkylene glycols with a molecular weight of 6,000 or less, such as polyethylene glycol, polyethylene glycol, poly i, 3 propylene glycol, and polyte
  • the polyester may be one or two structural units derived from a trifunctional or higher functional compound such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, or pyromellitic acid, if necessary. If you have a small amount, you can have it.
  • a trifunctional or higher functional compound such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, or pyromellitic acid, if necessary. If you have a small amount, you can have it.
  • Examples of the polycarbonate used in the layer (L3) include polycarbonate obtained by reacting a substantial dihydroxy compound with phosgene, a carbonic acid diester, or a halogen formate.
  • a dihydroxy compound as a raw material For example, 2,2 bis (4-hydroxyphenol) propane (hereinafter sometimes referred to as “bisphenol A”), tetramethylbisphenol A, tetrabromobisphenol A, bis (4-hydroxyphenol) p diisopropyl
  • Bisphenol A 2,2 bis (4-hydroxyphenol) propane
  • tetramethylbisphenol A tetrabromobisphenol A
  • Aromatic dihydroxy compounds such as benzene, hydroquinone, resorcinol and 4,4'-dihydroxyphenol can be mentioned, and among these, bisphenol A is preferred.
  • the polycarbonate may have one or more structural units derived from trihydroxy or higher polyhydroxy compounds in small amounts! /! /.
  • the polyamide used in the layer (L3) is not particularly limited as long as it has an amide bond in the polymer main chain and can be heated and melted.
  • Polyamides that can be used in the present invention include, for example, polyamides obtained by ring-opening polymerization of three-membered or more ratatams (polylatatams), polyamides obtained by polycondensation of ⁇ amino acids, and polycondensation of dibasic acids and diamines. The resulting polyamide can be used, and one or more of these polyamides can be used!
  • ratatam which is a raw material for polyamide
  • examples of the above-described ratatam include epsilon prolactam, enatoractam, force prilllatatam, lauryllatatam, a-pyrrolidone and the like.
  • specific examples of the above-mentioned ⁇ -amino acid that is a raw material of polyamide include 6-amino force proic acid, 7 aminoheptanoic acid, 9 aminononanoic acid, 11-aminoundecanoic acid and the like.
  • dibasic acid examples include aliphatic acids such as malonic acid, dimethylmalonic acid, succinic acid, 3,3 jetylsuccinic acid, glutaric acid, 2,2 dimethyldaltaric acid, adipic acid, sebacic acid, and suberic acid.
  • diamines include ethylene diamine, propylene diamine, 1,4 butane diamine, 1,6 hexane diamine, 1,8 octane diamine, 1,9-nonane diamine, 1,10-decandiamine, 1,12 Aliphatic diamines such as dodecane diamine, 2-methyl-1,5-pentane diamine, 3-methyl-1,5-pentane diamine; cycloaliphatic diamines such as cyclohexane diamine, methyl cyclohexane diamine, and isophorone diamine; p-phenol -Aromatic diamines such as -rangeamine, m-phenol-diamine, xylylenediamine, xylenediamine, 4,4'-diaminodiphenolinolemethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether .
  • Examples of the acrylic polymer used in the layer (L3) include an acrylic polymer mainly composed of a structural unit derived from a (meth) acrylic acid ester.
  • the proportion of structural units induced by (meth) acrylic acid ester force in the acrylic polymer is preferably 50% by weight or more, more preferably 80% by weight or more.
  • Examples of the (meth) acrylic acid ester constituting the acrylic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic.
  • Examples include alkyl esters of (meth) acrylic acid such as 2-ethylhexyl acid, and acrylic polymers have one or more of these (meth) acrylic acid ester-derived structural units. Can be.
  • the acrylic polymer may have one or more structural units derived from the unsaturated monomer force other than the (meth) acrylic acid ester, if necessary.
  • methacrylic resin may have a structural unit derived from a cyanobyl monomer such as (meth) acrylonitrile, preferably in a proportion of 50% by weight or less, and styrene, o-methylstyrene. , M-methylol styrene, p-methylol styrene, o chlorostyrene, m-chlorostyrene, p chlorostyrene, etc. Have it with, ok.
  • the salt-based polymer used in the layer (L3) a vinyl chloride homopolymer, a salted polymer having a structural unit derived from salted-bulu in a proportion of 70% by weight or more.
  • One or more of copolymers of vinyl and other copolymerizable monomers and chlorinated products thereof are preferably used.
  • the salt vinyl polymer is a salt vinyl copolymer
  • One or more copolymers of copolymerizable monomers such as maleimide are preferably used I can.
  • the degree of polymerization of the salt vinyl polymer is not particularly limited, but in general, the degree of polymerization is
  • the salt vinylidene polymer used in the polymer layer (L3) is a thermoplastic polymer having a structural unit derived from salt vinylidene in a proportion of 50% by weight or more. Is preferably used, and the thermoplastic polymer having a ratio of 70% by weight or more is more preferably used.
  • the salt vinylidene-based polymer is a copolymer of salt vinylidene and other monomers, such as salt vinylidene and butyl chloride, acrylonitrile, acrylate ester and acrylic acid. Copolymers with one or more other unsaturated monomers are preferably used.
  • the polymerization degree of the vinyl chloride vinylidene-based polymer is not particularly limited, but in general, those having a polymerization degree of 100 to 10,000 are preferably used, and those having a polymerization degree of 500 to 5,000 are preferably used.
  • layer of an ethylene acetate Bulle copolymer Sani ⁇ used in (L3) is E Ji Ren content 20 to 60 mole 0/0, preferably 25 to 60 mol%, a degree of saponification of 95 More than% is preferably used.
  • the ethylene acetate butyl copolymer cans have a melt index measured according to ASTM D-1238-65T of 0.1 to 25 gZlO (measured at 190 C, 2.16 kg load). It is more preferably 0.3 to 20 gZlO content from the viewpoint of moldability.
  • Typical examples of engineering plastics used in the layer (L3) include polyacetal (POM), polyphenylene ether (including modified polyphenylene ether), polysulfone (PSF), polyethersulfone ( PES), polyphenylene sulfide, polyarylene HU polymer), polyamideimide, polyetherketone (PEK), polyetheretherketone (PEEK), polyimide (PI), super engineering plastics such as liquid crystal polyester.
  • POM polyacetal
  • PSF polysulfone
  • PES polyethersulfone
  • PES polyethersulfone
  • PES polyphenylene sulfide
  • polyarylene HU polymer polyamideimide
  • PEK polyetherketone
  • PEEK polyetheretherketone
  • PI polyimide
  • the biological polymer used in the layer (L3) is a biological polymer made from "biomass” which is a raw material of biological origin such as plants and animals.
  • a typical example is poly-3-hydroxybutyric acid. (PHB), polylactic acid, polydaricholic acid, poly strength prolatatone, polyhydroxybutyrate, or a copolymer thereof, starch, cellulose, strength Examples include chitin, chitosan, kenaf, and natural rubber, which are ingredients such as shrimp shells.
  • Natural or artificial fibers used in the layer (L3) include glass fibers, carbon fibers, metal fibers, aromatic polyamide fibers, polyaramid fibers, alumina fibers, silicon carbide fibers, boron fibers, basalt fibers, and the like. Can be mentioned.
  • the metal used in the layer (L3) typically includes a metal material obtained by subjecting aluminum, iron, magnesium, titanium, an alloy thereof, or the like to a heat-adhesive surface treatment.
  • the thickness of each layer is not particularly limited and may be adjusted according to the type of polymer or material constituting each layer, the total number of layers in the laminated structure, the use of the laminated structure, and the like.
  • the thickness of the polymer layer (L1) is 10 m to 5 mm and the polymer layer (L)
  • the thickness of 2) should be 1 ⁇ m to lmm and the thickness of the polymer layer (L3) should be 10 ⁇ m to 5 mm. .
  • the total number of layers in the multilayer structure of the present invention is not particularly limited. Any may be used as long as it is a structure.
  • the laminated structure of the present invention includes a layer (L1), a layer (L2)
  • Examples of the laminated structure of the present invention include layer (LI) Z layer (L2) Z layer (L3) force three-layer structure; layer (L3) Z layer (LI) Z layer (L2) Z Layer (L3) Force 4 layer structure; Layer (LI) Z layer (L2) / Layer (L3) Z layer (L2) Z layer (L1) Force 5 layer structure; Layer (L3) Z layer (L2 ) Z layer (LI) Z layer (L2) Z layer (L3) force 5 layer structure; layer (L3) Z layer (LI) Z layer (L2) Z layer (L3) Z layer (L2) Z layer ( LI) Z layer (L3) 7 layer structure that also has force.
  • At least the polymer for layer (L1), the polymer for layer (L2) and the polymer or material for layer (L3) are melt-coextruded into a film, sheet or plate
  • a method of forming a laminated structure by forming and laminating simultaneously with extrusion molding of each layer (2) A film, a sheet, a plate, etc. constituting the layer (LI) are produced in advance, and a molded product such as a film, a sheet, a plate constituting the Z or layer (L3) is produced in advance, A layer prepared in advance while melt-extrusion of the polymer layer (L2) and, if one of the layers (L1) and (L3) is not preformed, it is also melt-extruded.
  • a molded product such as a film, a sheet or a plate constituting the layer (L1) and a molded product such as a film, a sheet or a plate constituting the layer (L3) are manufactured in advance, and the layer (L2)
  • the polymer for use is also formed into a film or sheet in advance, and the layer (L2) film or sheet is sandwiched between the layer (L1) molded product and the layer (L3) molded product and heated.
  • a method of producing a laminated structure by fusing a film or sheet for the layer (L2) below and bonding the layer (L1) and the layer (L3) together through the layer (L2);
  • the layer (L1) and the layer (L3) are bonded via the molten layer (L2), and the adhesive layer is organic. Since it does not contain a solvent, the desired laminated structure can be obtained without causing problems and troubles such as destruction of the natural environment by organic solvents, deterioration of the working environment, and recovery of the solvent.
  • the above-described method (1) by coextrusion molding requires fewer steps, increases productivity, and provides adhesion strength between layers (L1), (L2) and (C). It is preferable because it is high and a laminated structure without delamination can be obtained.
  • the laminated structure of the present invention is produced by the co-extrusion molding method
  • three or more extruders are connected to one die according to the number of layers of the laminated structure, and a plurality of weights are combined.
  • the coalescence can be produced by stacking together on the inside or outside of the die.
  • a T die, an annular die, or the like can be used as the die, and the shape and structure of the extruder and the die are not particularly limited.
  • the laminated structure of the present invention has the properties of the layer (L1), the layer (L2), and the layer (L3) constituting the layered structure. It can be used for various purposes, such as packaging materials for food and medical drugs; packaging materials for clothing; packaging materials for other products; for building materials such as wallpaper and decorative boards; Film for electrical insulation; base material for adhesive film and tape; marking film; film for agriculture; various items such as table cloth, raincoat, umbrella, curtain, cover, etc .; for laminating with metal plates and other materials Can be used for Industrial applicability
  • the laminated structure of the present invention has extremely high interlayer adhesive strength and is unlikely to delaminate. Therefore, packaging materials for foods and medical drugs, packaging materials for clothing, packaging materials for other products, wallpaper For building materials such as decorative panels, electrical insulation films, adhesive films and tape substrates, marking films, agricultural films, tablecloths, raincoats, umbrellas, curtains, covers, etc. It can be effectively used for various purposes such as laminating with metal plates and other materials.
  • MFR was measured according to ASTM D 1238 (230.C, load 2.16 kg). However, MFR is MFR measured under conditions of temperature 190 ° C and load 2.16kg.
  • the bending strength was measured according to ASTM D790 under the following conditions.
  • Test piece 12.7mm (width) X 3.2mm (thickness) X 127mm (length) Bending speed: 5mmZ min
  • Test piece thickness 1Z8 inch
  • Izod impact strength was measured under the following conditions in accordance with ASTM D256.
  • Test piece 12.7mm (width) X 3.2mm (thickness) X 64mm (length)
  • the notch was made by machining
  • the peeled-off state of the molded body was evaluated by a cello tape (registered trademark) peeling test (three times) in the vicinity of the gate part of the ASTM-1 test piece.
  • resins were used as polyolefin, polycarbonate resin, acrylic resin, bur polymer, polyphenylene oxide and the like.
  • Tuffmer A4050 (trade name) manufactured by Mitsui Chemicals, Inc. Ethylene 1-butene random copolymer, MFR Polyolefin (Al—4):
  • Noryl 115 (trade name) manufactured by Nippon Gichi Plastics Co., Ltd.
  • Nilil 646 (trade name) manufactured by Nippon Gichi Plastics Co., Ltd.
  • MODIPER A3400 (trade name) Polypropylene-Poly (styrene / acrylonitrile copolymer) block polymer
  • Tuftec H1043 (trade name) Polystyrene-poly (ethylene 'butene) polystyrene block copolymer
  • composition Specific Power The solubility parameter of the StZAN copolymer constituting the block (b) of the block polymer (A2-1) calculated was 21.9.
  • the solubility parameter of the PMMA constituting the block (b) of the block polymer (A2-2) calculated from the composition ratio was 19.1.
  • the molecular weight of the block (b) calculated by the composition ratio, the number average molecular weight of polypropylene, and the number of 2-bromoisobutyric acid groups per polypropylene molecular chain was 21,000.
  • composition Specific Power The solubility parameter 1 of the StZAN copolymer constituting the block (b) of the block polymer (A2-3) calculated was 23.1.
  • the halogen obtained in Production Example 1 above was placed in a 2 L glass reactor sufficiently purged with nitrogen.
  • Polypropylene lOOg, styrene (St) 720 ml, acrylonitrile (AN) 280 ml, glycidyl methacrylate (GMA) 60 ml, toluene 200 ml were added and stirred at 25 ° C.
  • 246 mg of copper (I) bromide and 0.72 ml of PMDETA were added, and polymerization was carried out at 90 ° C. for 2 hours.
  • the reaction solution was filtered, and the solid on the filter was washed with methanol and dried under reduced pressure to obtain 232.6 g of a solid polymer.
  • the solubility parameter 1 of the ASZGM A copolymer constituting the block (b) of the block polymer (A2-4) calculated from the composition ratio was 22.2.
  • the molecular weight of the block (b) calculated from the composition ratio, the number average molecular weight of polypropylene, and the number of 2-bromoisobutyric acid groups per one molecular chain of polypropylene was 45,000.
  • compositional power The calculated solubility parameter of the StZAN copolymer constituting the block (b) of the block polymer (A2-5) was 21.8.
  • the molecular weight of the block (b) calculated by the composition ratio, the number average molecular weight of polypropylene, and the number of grafts of bromine atoms per polypropylene molecular chain was 10,200.
  • Table 1 summarizes the polymer composition, the solubility parameter of the radical polymerization segment, the segment molecular weight, and the like in the above production example.
  • Rogenized polypropylene is placed in a glass polymerizer, and a toluene solution prepared so that styrene (St) and acrylonitrile (AN) are 4.9M and 2.1M, respectively, is added so that the polymer concentration is S93gZL. Then, deoxygenation operation was performed by nitrogen publishing. After that, a 1: 2 (mol ratio) toluene solution of copper bromide (I): N, N, N ', N ", N" -pentamethylgerylenetriamine (hereinafter abbreviated as "PMDETA”) was used. To the halogen content of the rogenized polypropylene, 2 equivalents of odorous copper (I) were added and heated and stirred.
  • PMDETA copper bromide
  • block polymer (A2-6) After 2.5 hours of polymerization at 105 ° C, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (A2-6)).
  • a propylene / 10-undecene-1-ol copolymer produced according to the method described in the examples of JP-A-2002-145944 is placed in a glass reactor, and hexane is added so that the polymer concentration becomes lOOgZL. Was added to form a slurry.
  • a 5-fold equivalent of 2-bromoisobutyric acid bromide was added to the amount of hydroxyl groups present in the polymer, the temperature was raised to 60 ° C., and the mixture was heated and stirred for 3 hours. Cool the reaction solution to 20 ° C at a cooling rate of 20 ° C Zh, Filtered off. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then filtered again.
  • the obtained white polymer was dried at 50 ° C. under reduced pressure of lOTorr for 10 hours.
  • polypropylene equivalent weight average molecular weight Mw 82,800
  • polypropylene equivalent number average molecular weight Mn 41,300
  • DSC measurement result shows melting point is 154 ° C
  • NMR analysis shows that it is derived from 2-bromoisobutyric acid bromide
  • the average number of bromine introduced ends was 1.3 Z chains.
  • 97% of the hydroxyl groups were halogenated polypropylene modified with 2 bromoisobutyric acid groups.
  • the obtained halogenated polypropylene was put into a glass polymerization vessel, styrene monomer was added so that the polymer concentration was 189 gZL, and deoxygenation operation was performed by nitrogen publishing. Then, a copper solution of copper bromide (I): PMDETA in a 1: 2 (molar ratio) toluene solution was added to give 1.5 equivalents of odorous copper (I) to the halogen content of the halogenated polypropylene.
  • a copper solution of copper bromide (I): PMDETA in a 1: 2 (molar ratio) toluene solution was added to give 1.5 equivalents of odorous copper (I) to the halogen content of the halogenated polypropylene.
  • the mixture was cooled in an ice bath to precipitate a polymer, filtered and washed with methanol.
  • the obtained polymer was dried at 80 ° C. under reduced pressure (10 Torr) to obtain a white polymer (herein
  • nBA n-butyl acrylate
  • MMA methyl methacrylate
  • the prepared toluene solution was added so that the polymer concentration became 30 g / L, and deoxygenation operation was performed by nitrogen publishing. Then, add a 1: 2 (mol ratio) toluene solution of copper bromide (PM): PMDETA to 3.5 equivalents of odorous copper (I) to the halogen content of the halogenated polypropylene. Warm, stir.
  • block polymer (A2-8) a white block copolymer (hereinafter referred to as block polymer (A2-8)).
  • block polymer (A2-9) After polymerization at 80 ° C. for 1.5 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (A2-9)).
  • Halogenated polypropylene synthesized by the method described in Production Example 8 is placed in a glass polymerizer and prepared so that n-butyl acrylate (nBA) and glycidyl methacrylate (GMA) are 3. OM and 0.30 M, respectively.
  • the toluene solution was added to a polymer concentration of 93 g / L, and deoxygenation was performed by nitrogen publishing.
  • a 1: 2 (mol ratio) toluene solution of copper (I) bromide: PMDE TA was added to the halogen content of the halogenated polypropylene to give 2 equivalents of odorous copper (I). Barking, warming 'stirring. After polymerization at 75 ° C.
  • block polymer (A2-10) a white polymer (hereinafter referred to as block polymer (A2-10)).
  • Toluene prepared by adding the halogenated polypropylene synthesized by the method described in Production Example 8 to a glass polymerization vessel so that styrene (St) and methyl methacrylate (MMA) were 5.9M and 0.6M, respectively.
  • the solution was prepared so that the polymer concentration became 87 gZL, and deoxygenation was performed by nitrogen publishing.
  • block polymer (A2-11) a white polymer (hereinafter referred to as block polymer (A2-11)).
  • Toluene prepared by adding the halogenated polypropylene synthesized by the method described in Production Example 8 to a glass polymerization vessel so that styrene (St) and methyl methacrylate (MMA) were 5.9M and 1.2M, respectively.
  • the solution was prepared so that the polymer concentration became 87 gZL, and deoxygenation was performed by nitrogen publishing.
  • block polymer (A2-12) a white polymer (hereinafter referred to as block polymer (A2-12)).
  • Toluene prepared by adding the halogenated polypropylene synthesized by the method described in Production Example 8 to a glass polymerization vessel so that styrene (St) and methyl methacrylate (MMA) were 5.9M and 1.8M, respectively.
  • the solution was prepared so that the polymer concentration became 87 gZL, and deoxygenation was performed by nitrogen publishing.
  • Table 2 summarizes the polymer compositions, radical polymerization segment solubility parameters, segment molecular weights, etc. in Production Examples 8 to 15 above. Table 2
  • the specific solubility parameter of the St polymer constituting the block (b) of the block polymer (A2-14) calculated was 18.7.
  • the molecular weight of block (b) calculated as composition ratio, number average molecular weight of polypropylene, and number power of 2-bromoisobutyric acid group per polypropylene molecular chain was 11,700.
  • Polypropylene (A1-1) 66. 7 parts by weight, block polymer prepared in Production Example 2 (A2-1) 4. 8 parts by weight, polycarbonate (B1-1) 28.5 parts by weight in a twin screw extruder
  • the mixture was melt-kneaded to prepare a pellet-shaped polyolefin resin composition.
  • the amount of room-temperature black mouth form insoluble component was measured.
  • ASTM test pieces were molded with an injection molding machine (IS55, manufactured by Toshiba Machine Co., Ltd.). The melt kneading conditions and injection molding conditions are shown below.
  • the content of the component derived from the block (b) contained in the room-temperature chloroform-insoluble component (hereinafter referred to as the block (b) content) and the physical properties of the molded product are as follows. Table 3 shows.
  • Kneading temperature 240 ° C
  • Injection molding machine Part number IS55, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 240 ° C
  • Example 1 except that the types and amounts of polyolefin, olefin-based block copolymer and polycarbonate resin, the kneading temperature during melt kneading and the cylinder temperature during injection molding were changed as shown in Table 3 or 4.
  • An ASTM test piece was molded. Tables 3 and 4 show the amount of insoluble component in the mouthpiece and the physical properties of the molded product.
  • the mixture was melt-kneaded to prepare a pellet-shaped polyolefin resin composition.
  • an ASTM test piece was molded with an injection molding machine (IS55, manufactured by Toshiba Machine Co., Ltd.). Izod specimens with machined notches were immersed in acetone or xylene solvent for 48 hours at room temperature, and Izod impact strength before and after immersion was measured.
  • Table 5 shows the kneading temperature, the molding temperature, and the measurement results. The ratio of Izod impact strength after immersion and before immersion was taken as the retention rate. The closer the retention rate is to 100%, the better the solvent resistance, which is close to the physical properties before immersion. [0278] [Comparative Examples 8 to 9]
  • the amount of polyolefin and polycarbonate resin, the kneading temperature at the time of melt kneading and the cylinder temperature at the time of injection molding were changed as shown in Table 5, and the polyolefin block copolymer produced in Production Example 2 (A2 — ASTM test pieces were molded in the same manner as in Example 15 except that 1) was not used.
  • A2 — ASTM test pieces were molded in the same manner as in Example 15 except that 1) was not used.
  • Izod impact strength before and after immersion in the solvent was measured. Table 5 shows the measurement results.
  • AST was performed in the same manner as in Example 16 except that the block polymer (A2-2) was used.
  • Table 6 shows the content of block (b) and the physical properties of the molded product.
  • Polypropylene (Al— 1) 66. 7 parts by weight, block polymer produced in Production Example 8 (A2— 6) 4.8 parts by weight and 28.5 parts by weight of vinyl polymer (B3-1) were melt-kneaded in a twin screw extruder to prepare a pelleted polyolefin resin composition. The amount of insoluble components at room temperature was measured using the obtained polyolefin resin composition. Further, the obtained polyolefin resin composition was dried overnight in a vacuum dryer at 80 ° C., and an ASTM test piece was molded using an injection molding machine. The melt-kneading conditions and injection molding conditions are shown below, and the physical properties of the molded products are shown in Table 7.
  • Kneading temperature 200 ° C
  • Injection molding machine Part number IS55, manufactured by Toshiba Machine Co., Ltd.
  • ASTM test specimens were molded in the same manner as in Example 17 except that the types and amounts of the polyolefin, block polymer, and bur polymer were changed. Tables 7 and 8 show the physical properties of the molded products.
  • ASTM specimens were molded in the same manner as in Example 17 except that the types and amounts of polyolefin and bur polymers were changed, copolymers H1043, A3400, and A3100 were used, and no block polymer was used. Tables 7 and 8 show the physical properties of the molded products.
  • ASTM test pieces were molded with an injection molding machine (IS 55, manufactured by Toshiba Machine Co., Ltd.). The melt-kneading conditions and the injection molding conditions are the same as in Example 1.
  • Table 9 shows the content of components derived from block (b) contained in the room-temperature chloroform-insoluble component, the C / C ratio, and the physical properties of the molded product.
  • Example 9 The same as Example 28, except that the types and amounts of polyolefin, olefin-based block copolymer and polyphenylene oxide, the kneading temperature during melt kneading and the cylinder temperature during injection molding were changed as shown in Table 9.
  • An ASTM test piece was molded.
  • Table 9 shows the block (b) content, C / C ratio, and physical properties of the molded product.
  • a monomer mixture of methyl acid (molar ratio 7: 3) was prepared so that the polymer concentration was 189 gZL, and deoxygenation was performed by nitrogen publishing. After that, add 1: 2 (mol ratio) toluene solution of copper bromide (PM): PMDETA to 3.0 equivalent of odorous copper (I) with respect to the halogen content of neurogenic polypropylene. Warm, stir. After polymerization at 100 ° C.
  • n BuA n-butyl acrylate
  • AN acrylonitrile
  • Polypropylene (Prime Polymer S 119) was placed in a glass reactor, and the mixture was stirred and heated at 120 ° C. for 2 hours with the black benzene added so that the polymer concentration became lOOgZL. So Thereafter, 2.5 parts by weight of N-bromosuccinimide was added to 100 parts by weight of polypropylene and reacted in a solution state at 100 ° C. for 2 hours. The reaction solution was poured into 4 L of acetone, and the precipitated polymer was filtered. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then collected again by filtration and dried under reduced pressure conditions of 80 ° C. and lOTorr for 10 hours.
  • This halogenated polypropylene is put into a glass polymerizer, and a toluene solution prepared so that acrylic acid-n-butyl (nBA) and glycidyl methacrylate (GMA) are 3.0 M and 0.30 M, respectively. In addition to the concentration of 93 g / L, deoxygenation was performed by nitrogen publishing.
  • Maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., below) 1 part by weight, tertiary butyl peroxybenzoate (Nippon Yushi Co., Ltd., trade name: Perbutyl Z) A solution of 0.5 part by weight dissolved in acetone. Dry blended.
  • Polymerization was conducted in the same manner as in Production Example 22 except that the amounts of butyl acrylate (nBuA), glycidyl methacrylate (GMA), and toluene were changed to 5.2 ml / l l. (Hereinafter referred to as block polymer (A2-21)). From the NMR analysis, the composition ratio (weight ratio) of PPZP (nBuA-Co-GMA) was 88/12 (wt%).
  • the reaction solution was cooled to 20 ° C. at a cooling rate of 20 ° C. Zh, and the polymer was filtered off.
  • the polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then filtered again.
  • the obtained white polymer was dried for 10 hours under reduced pressure at 50 ° C. and lOTorr. From the DSC measurement result, the melting point was 153.1 ° C, and from NMR analysis, the terminal introduced with bromine derived from 2-bromoisobutyric acid promide was an average of 7.5 Z-chains.
  • Table 10 summarizes the results of polymer composition analysis determined by 1 H-NMR.
  • the epoxy styrene (m, p mixture) used in the following examples was synthesized by the method described in Polymer 40 (9), 2411 (1 999).
  • Halogenated polypropylene obtained in Production Example 8 60 OgZL, n-butyl acrylate 495 ml / epoxystyrene (m, p-mixture) 210mlZL, acetone 295mlZL Concentrate in a 4-necked flask with condenser, 30 After nitrogen publishing for minutes, 0.8 mol ZL of PMDETA and cuprous bromide prepared in toluene were added to a concentration of 25 ml ZL and reacted at 55 ° C for 8 hours.
  • block polymer (A2-25) The solid obtained by filtering the reaction solution was washed several times with acetone and dried under reduced pressure at 60 ° C to obtain the target epoxy group-containing block polymer (hereinafter referred to as block polymer (A2-25)). Obtained.
  • Table 10 summarizes the composition analysis results of the polymer obtained from 1 H-NMR of the obtained block polymer.
  • the interfacial adhesive strength between the (L2) layer and the (L3) layer was determined under the conditions of a peeling atmosphere temperature of 23 ° C, a peeling speed of 500 mmZ, and a peel width of 10 mm. Obtained by peeling T-type. The results are shown in Table 11. Table 11 shows the mode of peeling.
  • the loss of grease means that the (L3) layer was broken and peeled off, and the cohesive peeling means that the (L2) layer was broken and peeled.
  • the (L2) layer remained in the (L3) layer and peeled, and ⁇ good '' means that the (L2) layer did not remain in the (L3) layer during peeling, and it peeled without exhibiting adhesive strength.
  • “No adhesion” means that the sample was peeled off at the sample preparation stage before the peel test.
  • Example 37 the conditions were changed to those shown in Table 11 except that the conditions were changed as shown in Table 11. A T-type peel test was performed. The results are shown in Table 11.
  • the maximum temperature during extrusion is set to random at 220 ° C for polypropylene, 230 ° C for the polymer composition, and 220 ° C for the ethylene butyl alcohol copolymer.
  • the interfacial adhesion strength between the (L2) layer and the (L3) layer was determined under the conditions of a peeling atmosphere temperature of 23 ° C, a peeling speed of 500 mmZ, and a peel width of 10 mm. Obtained by peeling T-type. The results are shown in Table 11. Table 11 shows the mode of peeling.
  • the interfacial adhesive strength between the (L2) layer and the (L3) layer was determined under the conditions of a peeling atmosphere temperature of 23 ° C, a peeling speed of 500 mmZ, and a peel width of 10 mm. Obtained by peeling T-type. The results are shown in Table 11. Table 11 shows the mode of peeling.
  • Example 37 a T-type peel test was performed in the same manner as in Example 37 except that the conditions shown in Table 11 were changed. The results are shown in Table 11.

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Abstract

Disclosed is a resin composition excellent in mechanical characteristics and solvent resistance. Specifically disclosed is a resin composition (C) containing a polyolefin (A1) and an olefin block polymer (A2), wherein the olefin block polymer (A2) contains a block (a) of a polyolefin component and a block (b) of a polymer residue of a vinyl monomer having a solubility parameter of 18-25 J/m as constituent units, and the block (a) and the block (b) are covalently bonded with each other. Also specifically disclosed is a multilayer body having a multilayer structure wherein an olefin polymer layer and a layer composed of another synthetic resin, a metal or the like are firmly bonded with each other via an adhesive layer. In this multilayer body, the adhesive layer contains the resin composition (C).

Description

明 細 書  Specification
ォレフィン系ブロックポリマーを含んでなる樹脂組成物およびその用途 技術分野  Resin composition comprising olefin-based block polymer and use thereof
[0001] 本発明は、ポリオレフインと極性樹脂とを含む榭脂組成物に関し、さら〖こ詳しくは、 耐衝撃性、引張強度等の機械的特性および耐溶剤性に優れた榭脂組成物に関す る。  [0001] The present invention relates to a resin composition comprising polyolefin and a polar resin. More specifically, the present invention relates to a resin composition excellent in mechanical properties such as impact resistance and tensile strength and solvent resistance. The
[0002] また、本発明は、該榭脂組成物からなる接着剤、フィルム又はシート、建材'土木用 材料、 自動車内外装材又はガソリンタンク、電気'電子部品、水性ェマルジヨン、溶剤 分散体、医療 ·衛生用材料、 日常雑貨類、および該榭脂組成物カゝらなる層を少なく ても 1層含む積層構造体に関する。  [0002] The present invention also relates to an adhesive comprising the resin composition, a film or sheet, a building material 'civil engineering material, an automobile interior / exterior material or a gasoline tank, an electric' electronic component, an aqueous emulsion, a solvent dispersion, a medical treatment. · Sanitary materials, daily goods, and laminated structures including at least one layer of the resin composition.
背景技術  Background art
[0003] ポリオレフインは、加工性、耐薬品性、電気的性質、機械的性質などに優れて 、る ため、押出成形品、射出成形品、中空成形品、フィルム、シートなどに加工され、各 種用途に用いられている。  [0003] Polyolefins are excellent in processability, chemical resistance, electrical properties, mechanical properties, etc., and are therefore processed into extrusion molded products, injection molded products, hollow molded products, films, sheets, etc. Used for applications.
[0004] し力しながらポリオレフインは、分子中に極性基を持たな 、、 V、わゆる無極性樹脂で あるため、金属をはじめ種々の極性物質との親和性に乏しぐ極性物質との接着また は極性樹脂とのブレンドが困難であった。 [0004] However, since polyolefin is a non-polar resin that does not have a polar group in its molecule, it adheres to polar substances that have poor affinity with metals and various polar substances. Also, blending with polar resins was difficult.
[0005] ポリオレフインの物性を改良する方法としては、モノマーの種類、モル比などを調整 する方法、ランダム、ブロックなどのモノマーの配列を変える方法、ポリオレフインに極 性モノマーをグラフト共重合する方法などがあり、従来から種々の方法が試みられて いる。 [0005] Methods for improving the physical properties of polyolefin include a method of adjusting the type and molar ratio of monomers, a method of changing the arrangement of monomers such as random and block, and a method of graft copolymerizing polar monomers to polyolefin. Various methods have been tried in the past.
[0006] ポリオレフインに極性モノマーをグラフト共重合する場合、ラジカル開始剤の存在下 にポリオレフインとラジカル重合性モノマーを反応させる方法が一般的に行われてい る力 このような方法によって得られたグラフト共重合体には、ラジカル重合性モノマ 一の単独重合体や未反応のポリオレフインが含まれる場合が多ぐまたグラフト構造も 不均一なものである。さらに、グラフト重合と共に、ポリマー鎖の架橋反応や分解反応 を伴うため、ポリオレフインの物性が大きく変化する場合が多力つた。 [0007] 上記のような架橋 ·分解反応を伴わずにポリオレフインと極性ポリマーのブロックポリ マーを合成する方法について、国際公開 WO98Z02472号パンフレットには、末端 に不飽和結合を有するポリオレフインにホウ素化合物を付加させた後に酸素で酸ィ匕 することによりラジカル重合活性種を形成させ、次 、でラジカル重合させる方法が記 載されている。 [0006] In the case of graft copolymerization of a polar monomer with polyolefin, a force is generally used to react the polyolefin with a radically polymerizable monomer in the presence of a radical initiator. The graft copolymer obtained by such a method is used. The polymer often contains a homopolymer of a radically polymerizable monomer or unreacted polyolefin, and the graft structure is not uniform. In addition, there are many cases where the physical properties of polyolefin greatly change because of the graft polymerization and the cross-linking reaction and decomposition reaction of the polymer chain. [0007] Regarding a method for synthesizing a block polymer of polyolefin and a polar polymer without the cross-linking / decomposition reaction as described above, International Publication WO98Z02472 pamphlet adds a boron compound to polyolefin having an unsaturated bond at the terminal. A method is described in which a radical polymerization active species is formed by oxidizing with oxygen after oxygenation, followed by radical polymerization.
[0008] 本発明者らはこのような従来技術のもと検討した結果、ポリオレフインセグメントと極 性榭脂セグメントとを含む特定のブロックポリマー力 上記のような問題を解決しうるこ とを見出した。  [0008] As a result of investigations based on such conventional techniques, the present inventors have found that a specific block polymer force including a polyolefin segment and a polar resin segment can solve the above-described problems. .
[0009] また、ポリオレフインは他の樹脂と積層して用いられることがある。ポリエステルフィル ムは機械的特性、耐薬品性などに優れており、それらの特性を活力ゝして、ポリエチレ ン、ポリプロピレン、その他のォレフィン系榭脂フィルムとの積層体の形態で様々な用 途に用いられている。ポリカーボネートフィルムは透明性、耐衝撃性などに優れ、ポリ メチルメタタリレートフィルムは透明性、耐候性、印刷適性などに優れており、それら の特性を活かして、種々のプラスチックフィルムとの積層が試みられている。エチレン •酢酸ビュル共重合体ケン化物フィルム、ポリ塩化ビ-リデンフィルム、ポリアミドフィ ルムは、ガスバリヤ一性に優れており、その高いガスノ リヤー性を活力して、ポリェチ レン、ポリプロピレン、などのようなヒートシール性やその他の性質に優れるプラスチッ クフィルムなどと積層して、包装材料などやその他の分野で巾広く用いられている。ま た、ポリ塩ィ匕ビュルフィルムは、その透明性、耐薬品性、印刷適性、機械的特性など に優れるので汎用プラスチックフィルムと積層することによって多くの産業界で有用な フィルムが提供されて 、る。  [0009] Polyolefin may be used by being laminated with other resins. Polyester film is excellent in mechanical properties and chemical resistance, and by utilizing these properties, it can be used in various applications in the form of laminates with polyethylene, polypropylene, and other polyolefin resin films. It is used. Polycarbonate film is excellent in transparency and impact resistance, and polymethylmethalate film is excellent in transparency, weather resistance, printability, etc. Utilizing these characteristics, lamination with various plastic films is attempted. It has been. EthyleneBuluric acetate copolymer saponified film, polyvinylidene chloride film, and polyamide film are excellent in gas barrier properties, and their high gas barrier properties are used to make polyethylene, polypropylene, etc. It is widely used in packaging materials and other fields by being laminated with plastic films that have excellent heat sealability and other properties. Polysalt film film is excellent in transparency, chemical resistance, printability, mechanical properties, etc., so it is useful for many industries by laminating with general-purpose plastic film. The
[0010] 従来、ォレフィン系榭脂などの基材と、ポリカーボネート榭脂、アクリル榭脂、ポリエ ステル樹脂などの極性基含有榭脂、またはアルミニウム等の金属との接着剤として、 スチレン ·共役ジェン ·スチレン系ブロック共重合体の水添物に無水マレイン酸をグラ フト重合させた変性ブロック共重合体、または該重合体と溶媒からなる接着剤が知ら れている（特許文献 2、 3)。また、熱可塑性ポリウレタンと芳香族ビニルイ匕合物 '共役 ジェン系重合体ブロック水添物の混合物を接着剤として用いる方法も開示されて ヽ る (特許文献 4)。しかし、これらの接着剤の接着力は十分でないことから、極性基含 有榭脂の基材とォレフイン系榭脂などの基材をさらに強力に接着せしめる接着剤が 求められている。 Conventionally, as an adhesive between a base material such as polyolefin resin and a polar group-containing resin such as polycarbonate resin, acrylic resin, polyester resin, or metal such as aluminum, styrene A modified block copolymer obtained by graft polymerization of maleic anhydride to a hydrogenated product of a styrene block copolymer or an adhesive comprising the polymer and a solvent is known (Patent Documents 2 and 3). Also disclosed is a method in which a mixture of thermoplastic polyurethane and aromatic vinyl compound “conjugated hydrogen polymer block hydrogenated product” is used as an adhesive (Patent Document 4). However, since the adhesive strength of these adhesives is not sufficient, There is a need for an adhesive that can more strongly bond a base material such as a resinous resin and a base material such as an olefin resin.
[0011] さて一般的には、上記したような積層フィルムの製造は、溶剤型接着剤を用いて各 プラスチックフィルム間の接着 ·積層を行う方法と、ホットメルト接着剤を用いて積層す る方法に二大別される。従来より、ポリエステルフィルム、ポリカーボネートフィルム、ァ クリル系重合体フィルム、エチレン 酢酸ビュル共重合体ケン化物フィルム、ポリ塩 化ビ-リデンフィルム、ポリ塩化ビュルフィルム等を、他のポリマーフィルムと積層する 場合には、溶剤型接着剤が汎用されてきたが、有機溶剤の使用による自然環境汚染 、作業環境の悪化や安全性の点で問題があり、溶剤型接着剤を用いない積層技術 が求められていた。また、極性基含有榭脂基材のうち、ポリカーボネートフィルムゃァ クリル系重合体フィルムなどは耐溶剤性が劣るため、選択可能な溶剤も限定されて ヽ た。以上の従来技術に鑑み、本発明者らは、ォレフィン系重合体を主要な構成成分 として含む層と、極性ビニル系プラスチック、エンジニアリングプラスチック、生物由来 ポリマー、熱可塑性エラストマ一、天然製または人工繊維、および金属カゝら選ばれる 少なくても 1種力もなる層力 特定のブロックポリマーを含むホットメルト型接着剤層を 介して、強力に接着されて ヽる積層構造を少なくとも一部有して ヽる積層構造体を開 発すべく鋭意検討を行い、本発明に到達したのである。  [0011] Now, in general, the production of the laminated film as described above is carried out by a method of adhering and laminating between plastic films using a solvent-type adhesive and a method of laminating using a hot melt adhesive. It is divided into two. Conventionally, when laminating polyester film, polycarbonate film, acrylic polymer film, ethylene acetate butyl copolymer saponified film, polychlorinated vinylidene film, polychlorinated butyl film, etc. with other polymer films Solvent-based adhesives have been widely used, but there are problems in terms of natural environmental pollution due to the use of organic solvents, work environment deterioration and safety, and a lamination technology that does not use solvent-based adhesives has been required. . Further, among polar group-containing resin base materials, polycarbonate films and acryl-based polymer films have poor solvent resistance, and therefore selectable solvents have been limited. In view of the above prior art, the present inventors have included a layer containing an olefin-based polymer as a main component, a polar vinyl-based plastic, an engineering plastic, a bio-derived polymer, a thermoplastic elastomer, a natural or artificial fiber, At least a layered structure that is strongly bonded via a hot-melt adhesive layer containing a specific block polymer. The inventors have intensively studied to develop a laminated structure and arrived at the present invention.
特許文献 1：国際公開 WO98Z02472号パンフレット  Patent Document 1: International Publication WO98Z02472 Pamphlet
特許文献 2 :特公平 4— 45532号公報  Patent Document 2: Japanese Patent Publication No. 4-45532
特許文献 3：特公昭 63— 65116号公報  Patent Document 3: Japanese Patent Publication No. 63-65116
特許文献 4：特開平 10— 202799号公報  Patent Document 4: Japanese Patent Laid-Open No. 10-202799
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0012] 本発明の課題は、耐衝撃性、引張強度等の機械的特性および耐溶剤性に優れた 榭脂組成物を提供することにある。 [0012] An object of the present invention is to provide a resin composition excellent in mechanical properties such as impact resistance and tensile strength, and solvent resistance.
[0013] また、本発明の他の課題は、ォレフィン系重合体を主要な構成成分として含む層と[0013] Another object of the present invention is to provide a layer containing an olefin-based polymer as a main constituent component.
、極性ビュル系プラスチック、エンジニアリングプラスチック、生物由来ポリマー、熱可 塑性エラストマ一、天然製または人工繊維、および金属から選ばれる少なくても 1種 力 なる層力 特定のォレフィン系ブロックポリマーを含むホットメルト型接着剤層を介 して、強力に接着されて ヽる積層構造を少なくても一部有して ヽる積層構造体を提 供することにある。 At least one selected from the following: polar bull plastics, engineering plastics, biological polymers, thermoplastic elastomers, natural or artificial fibers, and metals Powerful layer strength To provide a laminated structure that has at least part of a laminated structure that can be strongly bonded via a hot-melt adhesive layer containing a specific olefin-based block polymer. It is in.
課題を解決するための手段  Means for solving the problem
[0014] 本発明に係る榭脂組成物 (C)は、  [0014] The rosin composition (C) according to the present invention comprises:
ポリオレフイン（A1)と、  Polyolefin (A1),
ォレフィン系ブロックポリマー（A2)とを含んでなる榭脂組成物であって、 前記ォレフィン系ブロックポリマー（A2)力 ポリオレフイン成分であるブロック（a)と、 溶解度パラメータが 18〜25j/mの範囲にあるビュルモノマーの重合体残基である ブロック (b)を構成単位とし、前記ブロック (a)とブロック (b)とが互いに共有結合で結 ばれて 、ることを特徴として！/、る。  A resin composition comprising an olefin-based block polymer (A2), wherein the olefin-based block polymer (A2) force is a polyolefin component, and the solubility parameter is in the range of 18 to 25 j / m. Block (b), which is a polymer residue of a certain bull monomer, is a structural unit, and the block (a) and the block (b) are covalently bonded to each other! /
[0015] 本発明に係る榭脂組成物 (C)は、 [0015] The resin composition (C) according to the present invention comprises:
ポリオレフイン（Al) l〜98. 9重量0 /0と、 A polyolefin (Al) l~98. 9 wt 0/0,
ォレフィン系ブロックポリマー（A2) 0. 1〜50重量0 /0と、 And Orefin based block polymer (A2) 0. 1 to 50 weight 0/0,
ポリカーボネート榭脂 (bl)、アクリル系榭脂 (b2)、ビニル重合体 (b3)、およびポリ フエ-レンオキサイド (b4)力 選ばれる 1種以上の榭脂（B) 1〜98. 9重量％ (但し、 (Al)、 （A2)および (B)の合計量を 100重量％とする。）とからなることが好ましい。  Polycarbonate resin (bl), acrylic resin (b2), vinyl polymer (b3), and polyphenylene oxide (b4) force One or more selected resin (B) 1-98.9 wt% (However, the total amount of (Al), (A2) and (B) is 100% by weight).
[0016] 本発明では、前記ォレフィン系ブロックポリマー (A2)を構成するブロック（b)の該（ A2)中の含量が 0. 1〜70重量％であることも好ましい。  In the present invention, the content of the block (b) constituting the olefin-based block polymer (A2) in the (A2) is preferably 0.1 to 70% by weight.
[0017] また本発明では、前記ォレフィン系ブロックポリマー (A2)を構成するブロック (b)が 、（メタ）アクリル酸およびその誘導体、（メタ)アクリロニトリル、スチレンおよびその誘 導体、（メタ）アクリルアミドおよびその誘導体、マレイン酸およびその誘導体、マレイミ ドおよびその誘導体、およびビニルエステル類力 選ばれるビュルモノマーから誘導 される構成単位 1種以上の連鎖よりなることも好ましぐ  In the present invention, the block (b) constituting the olefin-based block polymer (A2) comprises (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, (meth) acrylamide and Its derivatives, maleic acid and its derivatives, maleimide and its derivatives, and vinyl esters. It is also preferred to consist of one or more structural units derived from the selected bull monomer.
前記ォレフィン系ブロックポリマー (A2)を構成するブロック (b) 1S スチレン、アタリ ロニトリル、 2—ヒドロキシェチルメタタリレート、グリシジルメタタリレートおよびメチルメ タクリレートから選ばれる 1種以上のビュルモノマーをラジカル（共)重合して得られる 重合体の残基であることも好まし 、。 [0018] さらに、本発明では、前記ォレフィン系ブロックポリマー (A2)を構成するブロック (bBlock constituting the olefin-based block polymer (A2) (b) 1S One or more butyl monomers selected from styrene, acrylonitrile, 2-hydroxyethyl methacrylate, glycidyl methacrylate and methyl methacrylate are combined with radicals (co-polymers). It is also preferred that it is a polymer residue obtained by polymerization. [0018] Furthermore, in the present invention, the block (b) constituting the olefin-based block polymer (A2)
)は、数平均分子量が 2,000〜200,000の範囲にあることも好ましい。 ) Preferably has a number average molecular weight in the range of 2,000 to 200,000.
[0019] また、本発明では、前記ォレフィン系ブロックポリマー (A2)を構成するブロック（a) 力 70°C以上の融点を有する結晶性ポリオレフイン残基であることも好ましぐ In the present invention, it is also preferable that the block (a) constituting the olefin-based block polymer (A2) is a crystalline polyolefin residue having a melting point of 70 ° C. or more.
榭脂組成物の室温クロ口ホルム不溶成分中のブロック (b)に由来する成分の含有 量が 0. 1〜70重量％であることも好ましぐ  It is also preferable that the content of the component derived from the block (b) in the room temperature black mouth form insoluble component of the greave composition is 0.1 to 70% by weight.
前記ォレフィン系ブロックポリマー (A2)は、ブロック (b)がブロック（a)—分子鎖当た り 0. 5〜5個結合していることも好ましい。  In the olefin-based block polymer (A2), it is also preferred that 0.5 to 5 blocks (b) are bonded per block (a) -molecular chain.
[0020] 本発明に係る、積層構造体は、 [0020] A laminated structure according to the present invention comprises:
ォレフィン系重合体を主要な構成成分として含む層（L1)、  Layer (L1) containing an olefin polymer as a main component,
上記榭脂組成物 (C)を含む層 (L2)、  A layer (L2) containing the above-mentioned rosin composition (C),
極性ビュル系プラスチック、芳香族ビニル系重合体、ポリエステル、ポリアミド、ポリ カーボネート、エンジニアリングプラスチック、生物由来ポリマー、熱可塑性エラストマ 一、天然製または人工繊維、および金属カゝら選ばれる少なくても 1種カゝらなる層（L3) 力 層（L1)Z層（L2)Z層（L3)の順に積層している構造を少なくとも一部に有する ことを特徴としている。  Polar bull plastic, aromatic vinyl polymer, polyester, polyamide, polycarbonate, engineering plastic, bio-derived polymer, thermoplastic elastomer, natural or artificial fiber, and metal at least one type selected It is characterized in that it has at least a part of a structure in which a layer (L3), a force layer (L1), a Z layer (L2), and a Z layer (L3) are laminated in this order.
[0021] 本発明では、前記榭脂組成物（C)力 ポリオレフイン (A1)と、ォレフィン系ブロック ポリマー (A2)とから構成されることも好ま 、。  In the present invention, it is also preferable that the resin composition (C) is composed of polyolefin (A1) and olefin-based block polymer (A2).
[0022] また、本発明では、前記榭脂組成物（C)を構成するォレフイン系ブロックポリマー（[0022] In the present invention, the olefin block polymer (C) constituting the resin composition (C)
A2)を構成するブロック (b)の示差走査型熱量計 (DSC)で測定したガラス転移温度Glass transition temperature measured by differential scanning calorimeter (DSC) of block (b) constituting A2)
(Tg)が 25°C以下であることも好ましぐ It is also preferable that (Tg) is 25 ° C or less.
前記榭脂組成物（C)を構成するォレフイン系ブロックポリマー (A2)を構成するプロ ック (a)の DSCで測定した融点 (Tm)に起因する吸熱ピークが 50°C以上である結晶 性ポリオレフイン残基であることも好ま 、。  Crystallinity in which the endothermic peak due to the melting point (Tm) measured by DSC of the block (a) constituting the olefin block polymer (A2) constituting the resin composition (C) is 50 ° C or higher. Also preferred is a polyolefin residue.
発明の効果  The invention's effect
[0023] 本発明に係る榭脂組成物は、耐衝撃性、引張強度、曲げ強度等の機械的特性お よび耐溶剤性に優れて!/、る。  The resin composition according to the present invention is excellent in mechanical properties such as impact resistance, tensile strength, bending strength, and solvent resistance.
[0024] 本発明に係る積層構造体は、ォレフィン系重合体を主要な構成成分として含む層 と、極性ビュル系プラスチック、ポリエステル、ポリアミド、ポリカーボネート、ェンジ- ァリングプラスチック、生物由来ポリマー、熱可塑性エラストマ一、天然製または人工 繊維、および金属カゝら選ばれる少なくても 1種からなる層との層間接着力に優れて ヽ る。 The laminated structure according to the present invention includes a layer containing an olefin-based polymer as a main constituent component. A layer consisting of at least one selected from polar-bule plastics, polyesters, polyamides, polycarbonates, engineering plastics, biological polymers, thermoplastic elastomers, natural or artificial fibers, and metal fibers. It has excellent interlayer adhesion.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0025] 以下、本発明に係るォレフィン系ブロックポリマーを含んでなる榭脂組成物および 積層構造体について具体的に説明する。  [0025] Hereinafter, the resin composition and laminated structure comprising the olefin-based block polymer according to the present invention will be specifically described.
[0026] まず、本発明に係るォレフィン系ブロックポリマーを含んでなる榭脂糸且成物につ！、て 説明する。 [0026] First of all, a resin composition comprising the olefin-based block polymer according to the present invention! I will explain.
[0027] 本発明に係る榭脂組成物 (C)は、  [0027] The rosin composition (C) according to the present invention comprises:
ポリオレフイン（A1)と、  Polyolefin (A1),
ォレフィン系ブロックポリマー（A2)とを含んでなる榭脂組成物であって、 前記ォレフィン系ブロックポリマー（A2)力 ポリオレフイン成分であるブロック（a)と、 溶解度パラメータが 18〜25j/mの範囲にあるビュルモノマーの重合体残基である ブロック (b)を構成単位とし、前記ブロック (a)とブロック (b)とが互いに共有結合で結 ばれている。  A resin composition comprising an olefin-based block polymer (A2), wherein the olefin-based block polymer (A2) force is a polyolefin component, and the solubility parameter is in the range of 18 to 25 j / m. The block (b), which is a polymer residue of a certain bull monomer, is used as a structural unit, and the block (a) and the block (b) are covalently bonded to each other.
[0028] 本発明に係る榭脂組成物 (C)は、 [0028] The rosin composition (C) according to the present invention comprises:
ポリオレフイン（A1)と、  Polyolefin (A1),
ォレフィン系ブロックポリマー（A2)と、  Olefin block polymer (A2),
ポリカーボネート榭脂 (bl)、アクリル系榭脂 (b2)、ビニル重合体 (b3)およびポリフ ェ-レンオキサイド (b4)力も選ばれる 1種以上の榭脂（B)とからなることが好ましい。  The polycarbonate resin (bl), the acrylic resin (b2), the vinyl polymer (b3), and the poly (ethylene oxide) (b4) are preferably composed of one or more types of resin (B) whose forces are also selected.
[0029] 以下、これらの成分について順次説明する。 [0029] Hereinafter, these components will be sequentially described.
[0030] 〔ポリオレフイン（Al)〕 [0030] [Polyolefin (Al)]
本発明で用いられるポリオレフイン (A1)は、炭素原子数 2〜20の aーォレフインか ら選ばれる少なくとも 1種のォレフィンの（共)重合体である。  The polyolefin (A1) used in the present invention is a (co) polymer of at least one olefin selected from a-olefin having 2 to 20 carbon atoms.
[0031] 炭素原子数 2〜20の α—ォレフインとしては、例えばエチレン、プロピレン、 1-ブテ ン、 2 ブテン、 1—ペンテン、 3—メチル 1—ブテン、 1—へキセン、 4—メチル 1 —ペンテン、 3—メチル 1—ペンテン、 1—オタテン、 1—デセン、 1—ドデセン、 1— テトラデセン、 1—へキサデセン、 1—ォクタデセン、 1—エイコセンなどの直鎖状また は分岐状の α -ォレフィン；例えばシクロペンテン、シクロヘプテン、ノルボルネン、 5 ーメチルー 2 ノルボルネン、テトラシクロドデセン、 2 メチル 1 ,4, 5, 8 ジメタノー 1 , 2, 3,4,4a,5, 8, 8a—ォクタヒドロナフタレンなどの環状ォレフィンが挙げられる。 [0031] Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2 butene, 1-pentene, 3-methyl 1-butene, 1-hexene, 4-methyl 1 —Pentene, 3-methyl 1-pentene, 1-otaten, 1-decene, 1-dodecene, 1— Linear or branched α-olefins such as tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2 methyl 1,4 , 5, 8 Dimethanol 1, 2, 3, 4, 4a, 5, 8, 8a—cyclic olefins such as octahydronaphthalene.
[0032] また、ポリオレフイン (A1)は、極性モノマー、例えば、アクリル酸、メタクリル酸、フマ ル酸、無水マレイン酸、ィタコン酸、無水ィタコン酸、ビシクロ（2,2, 1)—5—ヘプテン 2, 3 ジカルボン酸無水物などの α , β 不飽和カルボン酸、およびこれらのナトリ ゥム塩、カリウム塩、リチウム塩、亜鉛塩、マグネシウム塩、カルシウム塩などの a , j8 不飽和カルボン酸金属塩；アクリル酸メチル、アクリル酸ェチル、アクリル酸 n—プ 口ピル、アクリル酸イソプロピル、アクリル酸 n—ブチル、アクリル酸イソブチル、アタリ ル酸 tert ブチル、アクリル酸 2—ェチルへキシル、メタクリル酸メチル、メタクリル酸 ェチル、メタクリル酸 n—プロピル、メタクリル酸イソプロピル、メタクリル酸 n—ブチル、 メタクリル酸イソブチルなどの a , β 不飽和カルボン酸エステル；酢酸ビュル、プロ ピオン酸ビュル、カプロン酸ビュル、力プリン酸ビュル、ラウリン酸ビュル、ステアリン 酸ビュル、トリフルォロ酢酸ビュルなどのビュルエステル類；アクリル酸グリシジル、メ タクリル酸グリシジル、ィタコン酸モノグリシジルエステルなどの不飽和グリシジルエス テルなどが少量共重合されて!、てもよ!/、。  [0032] Polyolefin (A1) is a polar monomer such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene 2 , 3 α, β unsaturated carboxylic acids such as dicarboxylic acid anhydrides, and a, j8 unsaturated carboxylic acid metal salts such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, calcium salts; Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacrylic acid A, β such as ethyl, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Unsaturated carboxylic acid esters; butyl esters such as butyl acetate, propionate, caproate, force purate, laurate, stearate and trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, itacon A small amount of unsaturated glycidyl ester such as acid monoglycidyl ester is copolymerized!
[0033] また、ポリオレフイン (A1)は、ビュルシクロへキサン、ジェンまたはポリェンなどが少 量共重合されていてもよい。ジェンまたはポリェンとしては、炭素原子数 4〜30、好ま しくは 4〜20であり 2個以上の二重結合を有する環状又は鎖状の化合物が用いられ る。具体的には、ブタジエン、イソプレン、 4—メチル 1 , 3 ペンタジェン、 1 ,3 ぺ ンタジェン、 1 ,4 ペンタジェン、 1 ,5 へキサジェン、 1 ,4一へキサジェン、 1 ,3 へ キサジェン、 1 ,3—才クタジェン、 1 ,4ーォクタジェン、 1 ,5—才クタジェン、 1 ,6 オタ タジェン、 1 , 7—ォクタジェン、ェチリデンノルボルネン、ビュルノルボルネン、ジシク 口ペンタジェン； 7—メチルー 1 ,6—ォクタジェン、 4ーェチリデンー8—メチルー 1 , 7 —ノナジェン、 5,9—ジメチル一 1 ,4,8 デカトリェン；さらに芳香族ビ-ルイ匕合物、例 えばスチレン、 ο—メチノレスチレン、 m—メチルスチレン、 p—メチノレスチレン、 ο,ρ ジ メチルスチレン、 ο ェチルスチレン、 m—ェチノレスチレン、 p ェチルスチレンなどの モノまたはポリアルキルスチレン;メトキシスチレン、エトキシスチレン、ビュル安息香 酸、ビュル安息香酸メチル、ビュルべンジルアセテート、ヒドロキシスチレン、 ο クロ ロスチレン、 p—クロロスチレン、ジビュルベンゼンなどの官能基含有スチレン誘導体；[0033] Polyolefin (A1) may be copolymerized with a small amount of butylcyclohexane, gen or polyene. As the gen or polyene, a cyclic or chain compound having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl 1,3 pentagen, 1,3 pentane, 1,4 pentagen, 1,5 hexagen, 1,4 monohexagen, 1,3 hexagen, 1,3 —Tatagene, 1,4-octagen, 1,5—Tatagane, 1,6 Otatagen, 1,7—Octagen, Ethylidennorbornene, Burnorbornen, Dischikta Pentagen; 7—Methyl-1,6—Octagen, 4 --Ethylidene 8—Methyl-1,7—Nonogen, 5,9—Dimethyl 1,4,8 Decatriene; In addition, aromatic vinyl compounds such as styrene, ο—methylolstyrene, m-methylstyrene, p— Such as methylol styrene, ο, ρ dimethyl styrene, ο ethyl styrene, m-ethyl styrene, p ethyl styrene, etc. Mono- or polyalkyl styrene; functional group-containing styrene derivatives such as methoxy styrene, ethoxy styrene, bull benzoic acid, methyl bull benzoate, burbendyl acetate, hydroxy styrene, ο-chlorostyrene, p-chlorostyrene, dibulubenzene;
3—フエ-ルプロピレン、 4—フエニルプロピレン、 α—メチルスチレンなどが挙げられ る。 Examples include 3-phenylpropylene, 4-phenylpropylene, and α-methylstyrene.
[0034] ポリオレフイン（A1)のメルトフローレート（MFR : ASTM D1238： 230°C、荷重 2.  [0034] Melt flow rate of polyolefin (A1) (MFR: ASTM D1238: 230 ° C, load 2.
16kg)は、通常 0. 01〜200gZlO分、好ましくは 0. 1〜： LOOgZlO分である。  16 kg) is usually from 0.01 to 200 gZlO, preferably from 0.1 to LOOgZlO.
[0035] このようなポリオレフイン (A1)は従来公知の方法により製造することができる。 Such a polyolefin (A1) can be produced by a conventionally known method.
[0036] 本発明では、ポリオレフイン (A1)が立体規則性を有する場合には、シンジォタクテ イツクポリオレフイン、ァイソタクティックポリオレフインのいずれであっても良い。 In the present invention, when the polyolefin (A1) has stereoregularity, it may be either syndiotactic polyolefin or lysotactic polyolefin.
[0037] 本発明では、ポリオレフイン (A1)として、ポリエチレン、ポリプロピレンを用いること が好ましい。 [0037] In the present invention, polyethylene and polypropylene are preferably used as the polyolefin (A1).
[0038] 好ましいポリエチレンとしては、エチレン単独重合体、エチレン' aーォレフイン共重 合体などが挙げられる。エチレン' aーォレフイン共重合体は、例えばエチレンと炭素 原子数 4〜 12の atーォレフインとのランダム共重合体である。  [0038] Preferable polyethylene includes ethylene homopolymer, ethylene 'a-olefin copolymer and the like. The ethylene 'a-olefin copolymer is, for example, a random copolymer of ethylene and at-olefin having 4 to 12 carbon atoms.
[0039] ここで炭素原子数が 4〜 12の a—ォレフインとしては、たとえば 1—ブテン、 1—ぺ ンテン、 1—へキセン、 4—メチル 1—ペンテン、 1—オタテン、 1—デセン、 1—ドデ センなどが挙げられる。 [0039] Here, examples of a-olefin having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl 1-pentene, 1-octene, 1-decene, 1 —Dodecen.
[0040] このようなエチレン' aーォレフイン共重合体では、エチレンから導かれる構成単位 は、 65〜99重量％、好ましくは 75〜96重量％の割合で存在し、炭素原子数 4〜12 の aーォレフインから導かれる構成単位は、 1〜35重量0 /0、好ましくは 4〜25重量％ の割合で存在することが望ま 、。 [0040] In such an ethylene 'a-olefin copolymer, the structural unit derived from ethylene is present in a proportion of 65 to 99% by weight, preferably 75 to 96% by weight, and an a having 4 to 12 carbon atoms. constituent units derived from Orefuin is 1-35 weight 0/0, preferably desired to be present in a proportion of 4-25 wt%.
[0041] このエチレン' a—ォレフイン共重合体において、密度は、 0. 880〜0. 970g/c m3、好ましくは 0. 890〜0. 955g/cm3の範囲である。 [0041] In the ethylene 'a- Orefuin copolymer, density, 0. 880~0. 970g / cm 3 , preferably 0.890 to 0. Range of 955g / cm 3.
[0042] またエチレン · α—ォレフイン共重合体は、メルトフローレート（MFR : ASTM D12 38 : 190。C、荷重 2. 16kg)力 0. 01〜200gZlO分、好ましくは 0. 05〜50gZlO 分の範囲にある。  [0042] Further, the ethylene / α-olefin copolymer has a melt flow rate (MFR: ASTM D12 38: 190. C, load 2.16 kg) force of 0.01 to 200 gZlO, preferably 0.05 to 50 gZlO. Is in range.
[0043] 好まし!/、ポリプロピレンとしては、例えば、プロピレン単独重合体、プロピレン' ex ォレフィン共重合体、プロピレンと α—ォレフインと下式（1)で表される非共役ジェン との共重合体、さらには該共重合体の水添物などが挙げられる。 [0043] Preferable! / As polypropylene, for example, propylene homopolymer, propylene'ex Examples thereof include an olefin copolymer, a copolymer of propylene, α-olefin and a non-conjugated digen represented by the following formula (1), and a hydrogenated product of the copolymer.
[0044] [化 1]
Figure imgf000010_0001
… （ 1 ) [0044] [Chemical 1]
Figure imgf000010_0001
… (1)
[0045] [式（1)中、
Figure imgf000010_0002
R3および R4は、それぞれ独立に、水素原子または炭素原子数 1 〜6のアルキル基であり、 nは 1〜20の整数である。 ] [0045] [In the formula (1),
Figure imgf000010_0002
R 3 and R 4 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 20. ]
R3および R4の炭素原子数 1〜6のアルキル基としては、直鎖状および分岐 状のいずれであってもよい。具体的には、メチル基、ェチル基、 n プロピル基、イソ プロピル基、 n ブチル基、イソブチル基、 s ブチル基、 t ブチル基、 n—ペンチル 基、イソペンチル基、 t ペンチル基、ネオペンチル基、 n—へキシル基、イソへキシ ル基などが挙げられる。 The alkyl group having 1 to 6 carbon atoms of R 3 and R 4 may be linear or branched. Specifically, methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, s butyl group, t butyl group, n-pentyl group, isopentyl group, t pentyl group, neopentyl group, n —Hexyl group, isohexyl group and the like can be mentioned.
[0046] ポリプロピレンが共重合体である場合には、ランダム共重合体およびブロック共重 合体のいずれであってもよい。プロピレンと共重合させる aーォレフインとしては、ェ チレン、 1—ブテン、 4—メチル 1—ペンテン、 1—へキセン、 1—オタテン等を挙げ ることができ、これらの α—ォレフィンは、 1種単独でも 2種以上使用してもよい。  [0046] When polypropylene is a copolymer, it may be a random copolymer or a block copolymer. Examples of a-olefins to be copolymerized with propylene include ethylene, 1-butene, 4-methyl 1-pentene, 1-hexene, 1-octene, and the like. These α-olefins are used alone. However, two or more types may be used.
[0047] また、本発明においては、ポリプロピレンとして、 1種の重合体を単独使用する場合 のみならず、 2種以上の重合体を併用してもよい。  [0047] Further, in the present invention, not only when one polymer is used alone as polypropylene, but also two or more polymers may be used in combination.
[0048] ポリプロピレンの製造方法としては、特に限定されるものではなぐチーダラ 'ナッタ 触媒、メタ口セン系触媒等の周知の触媒を用いた周知の方法にて製造することがで きる。また、結晶性の重合体が好ましく使用でき、共重合体の場合にあっては、ランダ ム共重合体であっても、ブロック共重合体であってもよい。更に、成形性を満足し、成 形体としたときの使用に耐えうる強度を有するものであれば、立体規則性、分子量に ついても特段の制限はない。市販の榭脂をそのまま利用することも可能である。  [0048] The method for producing polypropylene is not particularly limited, and can be produced by a well-known method using a well-known catalyst such as a Cidara 'Natta catalyst or a meta-locene catalyst. A crystalline polymer can be preferably used, and in the case of a copolymer, it may be a random copolymer or a block copolymer. Furthermore, there are no particular restrictions on the stereoregularity and the molecular weight as long as they satisfy the moldability and have a strength that can be used when formed into a molded body. Commercially available rosin can be used as it is.
[0049] また、ポリプロピレンの融点（Tm)は、通常 150〜170°C、好ましくは 155〜167°C である。ポリプロピレンのメルトフローレート（MFR:ASTM D1238 : 230。C、荷重 2 . 16kg)は、通常 0. 3〜200gZlO分、好ましくは 0. 4〜： LOOgZlO分、さらに好まし くは 0. 5〜70gZlO分である。 [0049] The melting point (Tm) of polypropylene is usually 150 to 170 ° C, preferably 155 to 167 ° C. The melt flow rate of polypropylene (MFR: ASTM D1238: 230.C, load 2.16 kg) is usually 0.3 to 200 gZlO min, preferably 0.4 to: LOOgZlO min, more preferred Or 0.5 to 70 g ZlO.
[0050] ポリプロピレンとしては、このようなポリプロピレン榭脂の中では、榭脂の射出成形性 、耐熱剛性の観点から、プロピレン単独重合体、プロピレン 'エチレンブロック共重合 体を好ましく用いることができる。ポリプロピレンとしては、プロピレン由来の構成単位 が 50モル％以上、好ましくは 80モル％以上であるプロピレン系重合体 (A1)を好まし く用いることができる。 [0050] Among such polypropylene resins, propylene homopolymers and propylene / ethylene block copolymers can be preferably used among such polypropylene resins from the viewpoints of injection molding properties and heat-resistant rigidity. As the polypropylene, a propylene polymer (A1) having a propylene-derived structural unit of 50 mol% or more, preferably 80 mol% or more can be preferably used.
[0051] また、ポリプロピレンは、 13C—NMRで測定されるプロピレン単独重合部のアイソタ クチックペンタッド分率 (mmmm分率）が、好ましくは 96. 0%以上、さらに好ましくは 96. 5%以上、最も好ましくは 97. 0%以上であることが望ましい。ポリプロピレンにお けるプロピレン単独重合部のアイソタクチックペンタッド分率（mmmm分率）力^ 6. 0 %より低 、と、曲げ弾性率および Zまたは耐熱性が低下する場合がある。 [0051] In addition, polypropylene has an isotactic pentad fraction (mmmm fraction) of a propylene homopolymer portion measured by 13 C-NMR, preferably 96.0% or more, more preferably 96.5%. As mentioned above, it is most preferable that it is 97.0% or more. The isotactic pentad fraction (mmmm fraction) force of the propylene homopolymerized portion in polypropylene is less than 6.0%, and the flexural modulus and Z or heat resistance may decrease.
[0052] ここで、ァイソタクチックペンタッド分率（mmmm分率）とは、 A.Zambelliらによって、 Macromolecules, Vol.6,925 (1973)に記載された方法、すなわち13 C— NMR法（核磁 気共鳴法）によって測定される、ポリプロピレン分子鎖中のペンタッド単位でのァイソ タクチック分率であり、プロピレン単位が 5個連続してァイソタクチック結合したプロピ レンモノマー単位の分率である。 [0052] Here, the isotactic pentad fraction (mmmm fraction) is a method described by A. Zambelli et al. In Macromolecules, Vol. 6,925 (1973), that is, a 13 C-NMR method (nuclear magnetism). This is the isotactic fraction of pentad units in a polypropylene molecular chain, measured by the gas resonance method), and the proportion of propylene monomer units in which five propylene units are consecutively isotactically bonded.
[0053] 13C— NMR ^ベクトルにおけるピークの帰属は、 Macromolecules, Vol.8,687 (1975) の記載に基づいて行なわれる、 13C— NMRは、フーリエ変換 NMR [500MHz (水素 核測定時) ]装置を用いて、周波数 125MHZで、 20,000回の積算測定することによ り、シグナル検出限界を 0. 001まで向上させて測定することができる。 [0053] Assignment of peaks in the 13 C—NMR ^ vector is performed based on the description of Macromolecules, Vol. 8,687 (1975). 13 C—NMR is a Fourier transform NMR [at 500 MHz (when measuring hydrogen nuclei)] apparatus. By using, the signal detection limit can be improved to 0.001 by measuring 20,000 times at a frequency of 125 MHz.
[0054] 本発明ではポリオレフイン (A1)は、 2種以上組み合わせて用いてもよぐこのときの 組み合わせとしては、例えば結晶性のポリオレフインと、非晶性ないし低結晶性のポ リオレフインとの組み合わせが挙げられる。  [0054] In the present invention, the polyolefin (A1) may be used in combination of two or more types. For example, a combination of crystalline polyolefin and amorphous or low crystalline polyolefin may be used. Can be mentioned.
[0055] 〔ォレフイン系ブロックポリマー（A2)〕  [0055] Olefin Block Polymer (A2)]
本発明で用いられるォレフィン系ブロックポリマー（A2)は、ポリオレフイン成分であ るブロック（a)と溶解度パラメータが 18〜25jZmの範囲にあるビュルモノマーの重合 体残基であるブロック (b)とを有し、前記ブロック (a)とブロック (b)は共有結合によつ て結合した構造を有する。ォレフィン系ブロックポリマー (A2)は、ブロック (b)がブロ ック（a)—分子鎖当たり 0. 5〜5個結合していることが好ましい。またォレフィン系ブロ ックポリマー (A2)は、組成や分子量の異なる複数のブロック（a)およびブロック (b)を 有していてもよい。 The olefin-based block polymer (A2) used in the present invention has a block ( a ) which is a polyolefin component and a block (b) which is a polymer residue of a butyl monomer having a solubility parameter in the range of 18 to 25 jZm. The block (a) and the block (b) have a structure connected by a covalent bond. The olefin-based block polymer (A2) has a block (b) (A) —It is preferable that 0.5 to 5 bonds per molecular chain. The olefin-based block polymer (A2) may have a plurality of blocks (a) and blocks (b) having different compositions and molecular weights.
[0056] ォレフィン系ブロックポリマー（A2)は、ブロック（a)を 20〜99. 9重量部、好ましくは 30〜90重量部、ブロック（b)を 0. 1〜70重量部、好ましくは 10〜70重量部の量で 含有している。ブロック（a)、 （b)の含有量が上記範囲内にあるとォレフィン系ブロック ポリマー (A2)の相容化剤としての性能が向上し、島相の分散粒径が微細化し、機械 的強度が向上する。  [0056] The olefin-based block polymer (A2) has a block (a) of 20 to 99.9 parts by weight, preferably 30 to 90 parts by weight, and a block (b) of 0.1 to 70 parts by weight, preferably 10 to 10 parts by weight. Contains 70 parts by weight. When the content of the blocks (a) and (b) is within the above range, the performance as a compatibilizer of the olefin-based block polymer (A2) is improved, the dispersed particle size of the island phase is reduced, and the mechanical strength is increased. Will improve.
[0057] ォレフィン系ブロックポリマー（A2)は、 MFR(230°C、 2. 16kg荷重）が、 0. 01〜5 [0057] The olefin-based block polymer (A2) has an MFR (230 ° C, 2.16 kg load) of 0.01 to 5
OgZlO分の範囲にあることが好ましい。 It is preferably in the range of OgZlO minutes.
[0058] ここに、ブロック（a)は、例えば下記（al)〜（a5)力 なる群力 選ばれるポリオレフ インをハロゲンィ匕して得られるハロゲン変性ポリオレフイン (a' )に由来するセグメントと することができ、ブロック (b)は、ラジカル重合性単量体力も選ばれる 1種以上のモノ マーの単独重合体または共重合体である。 [0058] Here, the block (a) is a segment derived from halogen-modified polyolefin ( a ') obtained by halogenating selected polyolefins, for example, the following group forces (al) to (a5): The block (b) is a homopolymer or copolymer of one or more monomers whose radical polymerizable monomer power is also selected.
[0059] <ブロック（a) >  [0059] <Block (a)>
ォレフィン系ブロックポリマー（A2)を構成するブロック（a)としては、ポリオレフイン（ A1)と同様な構造を有するものを用いることが出来る。好ましくは融点が 70°C以上、 特に好ましくは 80〜180°Cの結晶性ポリオレフイン残基であることが好ましい。融点 が上記範囲内にあると耐熱性の高い榭脂組成物を得ることができる。  As the block (a) constituting the olefin-based block polymer (A2), those having the same structure as the polyolefin (A1) can be used. A crystalline polyolefin residue having a melting point of 70 ° C. or higher, particularly preferably 80 to 180 ° C. is preferred. When the melting point is within the above range, a resin composition having high heat resistance can be obtained.
[0060] 融点 (Tm)は例えば次のようにして測定される。試料 5mg程度を専用アルミパンに 詰め、パーキンエルマ一社製 DSCPyrislまたは DSC7を用い、 30°C力ら 200°Cま でを 320°CZminで昇温し、 200°Cで 5分間保持したのち、 200°Cから 30°Cまでを 1 0°CZminで降温し、 30°Cでさらに 5分間保持したのち、次いで 10°CZminで昇温 する際の吸熱曲線より求める。  [0060] The melting point (Tm) is measured, for example, as follows. About 5mg of sample is packed in a special aluminum pan, and using DSCPyrisl or DSC7 made by Perkin Elma Inc., the temperature is raised from 30 ° C to 200 ° C at 320 ° CZmin and held at 200 ° C for 5 minutes. Decrease the temperature from 200 ° C to 30 ° C at 10 ° C Zmin, hold it at 30 ° C for another 5 minutes, and then obtain it from the endothermic curve when raising the temperature at 10 ° C Zmin.
[0061] ォレフィン系ブロックポリマー（A2)は、ブロック（a)の数平均分子量が 5,000〜1,0 00,000、好ましくは 10,000〜500,000の範囲であり、ブロック（b)の数平均分子量 力 2,000〜200,000、好まし <ίま 5,000〜150,000の範囲でぁる重合体カ^好まし ヽ 。ブロック（a)の分子量が 1,000,000より高いと、ポリオレフイン (A1)と榭脂（B)の界 面にォレフィン系ブロックポリマー (A2)力分布しにくくなり、したがって、界面がはく 離しやすくなり機械的強度が低下する。分子量が 5,000より低いと、ポリオレフイン (A 1)ゃ榭脂（B)と、ォレフィン系ブロックポリマー (A2)との間での分子鎖同士のからみ 合いが少なくなり、機械的強度が低下する。 [0061] The olefin-based block polymer (A2) has a number average molecular weight of the block (a) in the range of 5,000 to 1,000,000, preferably 10,000 to 500,000, and the number average molecular weight of the block (b) in the range of 2,000 to 200,000. Preferable <polymer is preferred in the range of 5,000-150,000. If the molecular weight of the block ( a ) is higher than 1,000,000, the boundary between polyolefin (A1) and rosin (B) The olefin-based block polymer (A2) force is less likely to be distributed on the surface, and therefore the interface is easily peeled off and the mechanical strength is reduced. When the molecular weight is lower than 5,000, the molecular chains become less entangled between the polyolefin (A 1) resin (B) and the olefin-based block polymer (A2), and the mechanical strength decreases.
[0062] ォレフィン系ブロックポリマー（A2)を構成するブロック（a)は、ポリオレフインをハロ ゲンィ匕して得られるハロゲン変性ポリオレフインに由来するセグメントであってもよいし 、ラジカル重合開始基を有す極性基含有ォレフィン共重合体に由来するセグメントで あってもよいし、又、末端に周期律表 13族元素が結合したポリオレフインに由来する セグメントであってもよい。以下、ォレフィン系ブロックポリマー（A2)を構成するブロッ ク（a)力 ハロゲン変性ポリオレフインに由来するセグメントである場合について詳説 する。 [0062] The block (a) constituting the olefin-based block polymer (A2) may be a segment derived from halogen-modified polyolefin obtained by halogenating polyolefin, or a polar group having a radical polymerization initiation group The segment may be derived from a group-containing olefin copolymer, or may be a segment derived from a polyolefin having a group 13 element of the periodic table bonded to the terminal. Hereinafter, the block (a) force constituting the olefin-based block polymer (A2) will be described in detail for a segment derived from halogen-modified polyolefin.
[0063] なお、ォレフィン系ブロックポリマー (A2)を構成するブロック（a)がラジカル重合開 始基を有す極性基含有ォレフィン共重合体に由来するセグメントである場合は、本出 願人によって出願された特開 2002— 131620号公報にその詳細が開示されており 、また本願明細書の後半部で述べる「積層体」の項においてその技術内容が紹介さ れる。また末端に周期表第 13族元素が結合したポリオレフインに由来するセグメント は本出願人によって出願された WO01Z053369号パンフレットに開示されている。  [0063] If the block (a) constituting the olefin-based block polymer (A2) is a segment derived from a polar group-containing olefin copolymer having a radical polymerization initiation group, an application is filed by the present applicant. The details are disclosed in the published Japanese Patent Application Laid-Open No. 2002-131620, and the technical contents are introduced in the section of “Laminate” described later in this specification. A segment derived from polyolefin having a group 13 element of the periodic table bonded to the terminal is disclosed in a pamphlet of WO01Z053369 filed by the present applicant.
[0064] ォレフィン系ブロックポリマー（A2)を構成するブロック（a)は、以下の（al)〜（a5) 力もなる群力も選ばれるポリオレフイン (a")をノ、ロゲンィ匕して得られるハロゲン変性ポ リオレフイン (a，）に由来するセグメントとすることができる。  [0064] The block (a) constituting the olefin-based block polymer (A2) has the following (al) to (a5) halogen-modified products obtained by applying and / or roving polyolefin (a "), which also has a group force selected as a force It can be a segment derived from polyolefin (a,).
[0065] ここでポリオレフイン（a")は数平均分子量が 5,000〜1,000,000の範囲が好ましく 、 10,000〜500,000力より好まし!/ヽ。  Here, the polyolefin (a ") preferably has a number average molecular weight in the range of 5,000 to 1,000,000, more preferably 10,000 to 500,000 force! / 000.
[0066] またポリオレフイン（a")は分子量分布 (Mw/Mn)が 1. 5以上である。  [0066] Polyolefin (a ") has a molecular weight distribution (Mw / Mn) of 1.5 or more.
[0067] ここでポリオレフイン（a，，）をノヽロゲン化して得られるハロゲン変性ポリオレフイン（a， ) について説明する。  Here, the halogen-modified polyolefin (a,) obtained by halogenating the polyolefin (a,) will be described.
[0068] (al)は CH =CH— C H (xは 0または正の整数）で示される α—ォレフインの単  [0068] (al) is a single α-olefin defined by CH = CH— C H (x is 0 or a positive integer).
2 2χ+1  2 2χ + 1
独重合体または共重合体 (以下「 (共)重合体 (al)」とも 、う。 )であり、  Homopolymer or copolymer (hereinafter also referred to as “(co) polymer (al)”),
(a2)は CH =CH-C H (xは 0または正の整数）で示される α—ォレフインと芳  (a2) is the same as α-olefin and CH = CH-C H (x is 0 or a positive integer).
2 2χ+1 香環を有するモノォレフィンィ匕合物との共重合体 (以下「共重合体 (a2)」とも 、う。）で あり、 2 2χ + 1 A copolymer with a monoolefin-containing compound having an aromatic ring (hereinafter also referred to as “copolymer (a2)”),
(a3)は CH =CH-C H (xは 0または正の整数）で示される α—ォレフインと下  (a3) is CH = CH-C H (where x is 0 or a positive integer)
2 2χ+1  2 2χ + 1
記一般式（2)で表される環状モノォレフィン化合物との共重合体 (以下「共重合体 (a 3)」ともいう。）であり、  A copolymer with a cyclic monoolefin compound represented by the general formula (2) (hereinafter also referred to as “copolymer (a 3)”),
(a4)は CH =CH-C H (xは 0または正の整数）で示される α—ォレフインと不  (a4) is the same as the α-olefin defined by CH = CH-C H (x is 0 or a positive integer).
2 2χ+1  2 2χ + 1
飽和カルボン酸またはその誘導体とのランダム共重合体 (以下「共重合体 (a4)」とも いう。）であり、  A random copolymer with a saturated carboxylic acid or a derivative thereof (hereinafter also referred to as “copolymer (a4)”),
(a5)は前記 (al)〜（a4)で表される重合体を不飽和カルボン酸またはその誘導体 により、変性したポリオレフイン（以下「変性ポリオレフイン (a5)」ともいう。）である。  (a5) is a polyolefin obtained by modifying the polymer represented by (al) to (a4) with an unsaturated carboxylic acid or a derivative thereof (hereinafter also referred to as “modified polyolefin (a5)”).
[0069] [化 2] [0069] [Chemical 2]
Figure imgf000014_0001
Figure imgf000014_0001
[0070] 上記一般式（2)において、 nは 0または 1であり、 mは 0または正の整数であり、 qは 0 または 1である。なお qが 1の場合には、 Raおよび Rbは、それぞれ独立に、下記の原 子または炭化水素基を表し、 qが 0の場合には、それぞれの結合手が結合して 5員環 を形成する。 In the above general formula (2), n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, R a and R b each independently represent the following atom or hydrocarbon group, and when q is 0, each bond is bonded to form a 5-membered ring. Form.
[0071] 上記一般式（2)において、 Ri〜R18ならびに Raおよび Rbは、それぞれ独立に、水素 原子、ハロゲン原子および炭化水素基よりなる群力 選ばれる原子または基を表す。 In the above general formula (2), Ri to R 18 and R a and R b each independently represent an atom or group selected from the group force consisting of a hydrogen atom, a halogen atom and a hydrocarbon group.
[0072] ここで、ハロゲン原子は、フッ素原子、塩素原子、臭素原子またはヨウ素原子である 。また炭化水素基としては、それぞれ独立に、通常、炭素原子数 1〜20のアルキル 基、炭素原子数 1〜20のハロゲンィ匕アルキル基、または炭素原子数 3〜15のシクロ アルキル基が挙げられる。より具体的には、アルキル基としては、メチル基、ェチル基 、プロピル基、アミル基、へキシル基、ォクチル基、デシル基、ドデシル基、ォクタデシ ル基などが挙げられ、ハロゲン化アルキルとしては、上記のようなアルキル基を形成 している水素原子の少なくとも一部がフッ素原子、塩素原子、臭素原子またはヨウ素 原子で置換された基が挙げられ、シクロアルキル基としては、シクロへキシル基など が挙げられる。 [0072] Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C1-C20 halogenoalkyl group, or a C3-C15 cycloalkyl group is mentioned each independently independently. More specifically, examples of the alkyl group include a methyl group and an ethyl group. , A propyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, and the like. As the alkyl halide, at least one of the hydrogen atoms forming the alkyl group as described above is used. Examples thereof include groups in which a part is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and examples of the cycloalkyl group include a cyclohexyl group.
[0073] これらの基は低級アルキル基を含有して 、てもよ 、。さらに上記一般式（2)にお ヽ て、 R15と R16とが、 R17と R18とが、 R15と R17とが、 R16と R18とが、 R15と R18とが、あるいは R16 と R17とがそれぞれ結合して (互いに共同して）、単環または多環を形成していてもよ い。ここで形成される単環または多環としては、具体的に以下にようなものが挙げられ る。 [0073] These groups may contain a lower alkyl group. Furthermore, in the above general formula (2), R 15 and R 16 are R 17 and R 18 , R 15 and R 17 are R 16 and R 18 , R 15 and R 18 are Or R 16 and R 17 may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring. Specific examples of the monocyclic or polycyclic ring formed here include the following.
[0074] [化 3]  [0074] [Chemical 3]
Figure imgf000015_0001
Figure imgf000015_0001
[0075] なお上記例示において、 1および 2の番号を賦した炭素原子は、上記一般式（2)に お!、て、それぞれ 5 (R16)または R17 (R18)が結合して 、る炭素原子を表す。 [0075] In the above examples, the carbon atoms assigned numbers 1 and 2 are bonded to 5 (R 16 ) or R 17 (R 18 ) in the general formula (2), respectively. Represents a carbon atom.
[0076] 上記一般式（2)で表される環状ォレフィンとしては、具体的には、ビシクロ [2.2.1]へ ブト- 2-ェン誘導体、トリシクロ [4.3.0.12'5]- 3-デセン誘導体、トリシクロ [4.3.0.12'5]- 3- ゥンデセン誘導体、テトラシクロ [4.4.0.12'5.17'1()]-3-ドデセン誘導体、ペンタシクロ [7.4 .0.12,5.19,12.08,13] -3-ペンタデセン誘導体、ペンタシクロ [6.5.1.13,6.02,7.09,13] -4-ペンタ デセン誘導体、ペンタシクロ [8.4.0.12'3.19'12.08'13]- 3-へキサデセン誘導体、ペンタシ クロ [6.6.1.13'6.02'7.09'14]-4-へキサデセン誘導体、ペンタシクロペンタデカジエン誘 導体、へキサシクロ [6.6.1.13,6.110'13.02,7.09,14] -4-ヘプタデセン誘導体、ヘプタシクロ [ 8.7.0.13'6.l10'17.l12'15.02,7.01W6 ]-4-エイコセン誘導体、ヘプタシクロ- 5-エイコセン誘 導体、ヘプタシクロ [8.8.0.14'7.11W8.113'16.03'8.012'17]- 5-ヘンエイコセン誘導体、ォクタ シクロ [8.8.0.12'9.14'7.11W8.113'16.03'8.012'17]— 5—ドコセン誘導体、ノナシクロ [10.9.1.14'7.1 20 15'18.。3'8.。2'1。.。12'21.。14'19]— 5—ペンタコセン誘導体、ノナシクロ [10.10.1.15'8.114'21.116 .o2'11^4'9^13'2^15 ]^-へキサコセン誘導体などが挙げられる。 [0076] As the cyclic Orefin represented by the general formula (2) include, but-bicyclo [2.2.1] - 2-E down derivatives, tricyclo [4.3.0.1 2 '5] - 3- decene derivatives, tricyclo [4.3.0.1 2 '5] - 3- Undesen derivatives, tetracyclo [4.4.0.1 2' 5 .1 7 ' 1 ()] -3- dodecene derivatives, pentacyclo [7.4 .0.1 2,5 .1 9,12 .0 8,13] -3-pentadecene derivatives, pentacyclo [6.5.1.1 3,6 .0 2,7 .0 9,13] -4- penta-decene derivatives, pentacyclo [8.4.0.1 2 '3. 1 9 '12.0 8' 13] - Kisadesen derivatives to 3, Pentashi black [6.6.1.1 3 '6 .0 2' 7 .0 9 '14] -4- to Kisadesen derivatives, penta cyclopentadiene decadiene derivative conductor, to Kisashikuro [6.6.1.1 3,6 .1 10 '13 .0 2,7 .0 9,14] -4- heptadecene derivatives, heptacyclo [8.7.0.1 3' 6 .l 10 ' 17 .l 12' 15 .0 2,7 .0 1W6] -4- eicosene derivatives, heptacyclo - 5-eicosene derivative conductors, Heputashi B [8.8.0.1 4 '7 .1 1W8 .1 13' 16 .0 3 '8 .0 12' 17] - 5- heneicosene derivatives, Okuta cyclo [8.8.0.1 2 '9 .1 4' 7 .1 1W8 .1 13 '16.0 3' 8.0 12 '17] - 5-docosenoic derivatives, Nonashikuro [10.9.1.1 4' 7 .1 20 15 '18 .. 3 '8 .. 2 ' 1 . .. 12 '21 .. 14 '19] - 5-pentacosene derivatives, Nonashikuro [10.10.1.1 5' 8 .1 14 ' 21 .1 16 .o 2' 11 ^ 4 '9 ^ 13' 2 ^ 15] ^ - such Kisakosen derivatives thereof to It is done.
[0077] 上記のような一般式（2)で表される環状モノォレフィンィ匕合物は、シクロペンタジェ ンと対応する構造を有するォレフィン類とを、ディールス 'アルダー反応させることによ つて製造することができる。これらの環状ォレフィンは、単独であるいは 2種以上組み 合わせて用いることができる。  [0077] The cyclic monoolefin-containing compound represented by the general formula (2) as described above is produced by subjecting cyclopentagen and olefins having a corresponding structure to Diels' Alder reaction. Can do. These cyclic olefins may be used alone or in combination of two or more.
[0078] 《（共)重合体 (al) »  [0078] << (Co) polymer (al) »
(共）重合体（al)において、 CH =CH-C H (xは 0または正の整数）で示され  In (co) polymer (al), CH = CH-C H (x is 0 or a positive integer)
2 2x+l  2 2x + l
る a—ォレフインとしては、具体的には、エチレン、プロピレン、 1—ブテン、 1—ペン テン、 3—メチルー 1ーブテン、 1一へキセン、 4ーメチルー 1 ペンテン、 3 メチル — 1—ペンテン、 1—オタテン、 1—デセン、 1—ドデセン、 1—テトラデセン、 1—へキ サデセン、 1—ォクタデセン、 1—エイコセンなどの炭素原子数 2〜20の直鎖状また は分岐状の α—ォレフインが挙げられる。これらの例示ォレフィン類の中では、ェチ レン、プロピレン、 1—ブテン、 1—へキセン、 4—メチル 1—ペンテン、 1—オタテン 力も選ばれる少なくても 1種以上のォレフィンを使用することが好ましい。  Specific examples of a-olefin include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1- Examples include linear or branched α-olefins having 2 to 20 carbon atoms such as otaten, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. . Among these exemplified olefins, ethylene, propylene, 1-butene, 1-hexene, 4-methyl 1-pentene, and 1-octene are selected, and at least one olefin can be used. preferable.
[0079] (共)重合体 (al)としては、上記の aーォレフインを単独重合または共重合して得ら れるものであれば特に制限はないが、低密度ポリエチレン、中密度ポリエチレン、高 密度ポリエチレン、直鎖状低密度ポリエチレン、超高分子量ポリエチレンなどのェチ レン系重合体、プロピレンホモポリマー、プロピレンランダムコポリマー、プロピレンブ ロックコポリマーなどのプロピレン系重合体、ポリブテン、ポリ（4ーメチルー 1 ペンテ ン）、ポリ（1一へキセン）、エチレン プロピレン共重合体、エチレンーブテン共重合 体、エチレン一へキセン共重合体、エチレン オタテン共重合体、エチレン一（4ーメ チルー 1 ペンテン）共重合体、プロピレンーブテン共重合体、プロピレン一（4ーメ チルー 1 ペンテン）共重合体、プロピレン一へキセン共重合体、プロピレン ォクテ ン共重合体などが好ましく挙げられる。特にプロピレン由来の構成単位が 50モル％ 以上、好ましくは 80モル0 /0以上であるプロピレン系重合体が好ましい。 [0079] The (co) polymer (al) is not particularly limited as long as it is obtained by homopolymerization or copolymerization of the above-mentioned a-olefin, but low density polyethylene, medium density polyethylene, and high density polyethylene are not particularly limited. Ethylene polymers such as linear low density polyethylene and ultra high molecular weight polyethylene, propylene polymers such as propylene homopolymer, propylene random copolymer and propylene block copolymer, polybutene, poly (4-methyl-1 pentene) , Poly (1 hexene), ethylene propylene copolymer, ethylene-butene copolymer, ethylene monohexene copolymer, ethylene otaten copolymer, ethylene mono (4-methyl-1-pentene) copolymer, propylene- Butene copolymer, propylene mono (4-methyl-1-pentene) copolymer, propylene monohexene Copolymers, propylene Okute down copolymers preferably. In particular constitutional unit derived from propylene 50 mol% or more, preferably a propylene-based polymer is preferably 80 mol 0/0 above.
[0080] 《共重合体（a2)》  [0080] << Copolymer (a2) >>
共重合体（a2)にお!/、て、 CH = CH— C H (xは 0または正の整数）で示される  In copolymer (a2)! /, CH = CH— C H (x is 0 or a positive integer)
2 2x+l aーォレフインとしては、上記（共)重合体 (al)の項で記載したものと同様の α—ォ レフインが挙げられ、芳香環を有するモノォレフィンィ匕合物としては、具体的には、ス チレン、ビニノレトノレェン、 α—メチノレスチレン、クロノレスチレン、スチレンスノレホン酸及 びその塩等のスチレン系化合物やビニルピリジンなどが挙げられる。共重合体 (a2) としては、上記の aーォレフインと芳香環を有するモノォレフィンィ匕合物とを共重合し て得られるものであれば特に制限はな 、。 2 2x + l Examples of a-olefin include α-olefins similar to those described in the above-mentioned (co) polymer (al), and specific examples of monoolefin-containing compounds having an aromatic ring include styrene, Examples thereof include styrene compounds such as vinylolene, α -methylolstyrene, chronolestyrene, styrene sulphonic acid and its salts, and vinylpyridine. The copolymer (a2) is not particularly limited as long as it is obtained by copolymerization of the above-mentioned a-olefin and a monoolefin-containing compound having an aromatic ring.
[0081] 《共重合体（a3)》 [0081] << Copolymer (a3) >>
共重合体（a3)にお!/、て、 CH = CH— C H (xは 0または正の整数）で示される  Copolymer (a3) is indicated by! /, CH = CH— C H (x is 0 or a positive integer)
2 2x+l  2 2x + l
aーォレフインとしては、上記（共)重合体 (al)の項で記載したものと同様の α—ォ レフインが挙げられ、上記一般式（2)で表される環状モノォレフィンィ匕合物力 誘導さ れる構成単位は、下記一般式（3)で示される。  Examples of the a-olefin include α-olefins similar to those described in the section of the (co) polymer (al), and a structure in which a cyclic monoolefin-compound force represented by the general formula (2) is induced. The unit is represented by the following general formula (3).
[0082] [化 4] [0082] [Chemical 4]
Figure imgf000017_0001
Figure imgf000017_0001
[0083] 式（3)において、 n、 m、 q、 R1〜R18ならびに Ra、 Rbは式（2)と同じ意味である。 In Formula (3), n, m, q, R 1 to R 18, and R a and R b have the same meaning as in Formula (2).
[0084] 《共重合体 (a4) » [0084] << Copolymer (a4) »
共重合体（a4)にお!/、て、 CH = CH— C H (xは 0または正の整数）で示される  In copolymer (a4)! /, CH = CH— CH (where x is 0 or a positive integer)
2 2x+l  2 2x + l
aーォレフインとしては、上記（共)重合体 (al)の項で記載したものと同様の α—ォ レフインが挙げられ、不飽和カルボン酸またはその誘導体としては、例えば、不飽和 モノカルボン酸およびその誘導体や不飽和ジカルボン酸およびその誘導体、ビニル エステル類が挙げられ、具体的には、 （メタ)アクリル酸、 （メタ）アクリル酸エステル、 ( メタ）アクリル酸ノヽライド、 （メタ）アクリル酸アミド、マレイン酸、マレイン酸無水物、マレ イン酸エステル、マレイン酸ハライド、マレイン酸アミド、マレイン酸イミド、酢酸ビュル や酪酸ビュルなどの脂肪族ビニルエステル類などが挙げられる。共重合体 (a4)とし ては、上記の α—ォレフインと不飽和カルボン酸またはその誘導体とのランダム共重 合体であれば特に制限はないが、前記 α ォレフインカも誘導される構成単位を 50 モル％以上含有するものが好ま 、。 Examples of the a-olefin include α-olefins similar to those described in the above-mentioned (co) polymer (al), and examples of the unsaturated carboxylic acid or its derivative include unsaturated monocarboxylic acid and its Derivatives, unsaturated dicarboxylic acids and derivatives thereof, and vinyl esters, such as (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid halide, (meth) acrylic acid amide, Maleic acid, maleic anhydride, maleic acid ester, maleic acid halide, maleic acid amide, maleic acid imide, acetic acid butyl And aliphatic vinyl esters such as butyl butyrate. The copolymer (a4) is not particularly limited as long as it is a random copolymer of the above-mentioned α-olefin and an unsaturated carboxylic acid or derivative thereof, but 50 mol of the structural unit from which the α-olefin is also derived. Those containing more than 50% are preferred.
[0085] <変性ポリオレフイン（a5) >  [0085] <Modified polyolefin (a5)>
変性ポリオレフイン (a5)において、不飽和カルボン酸またはその誘導体としては、 具体的には、マレイン酸、マレイン酸無水物、マレイン酸エステル、マレイン酸ハライ ド、マレイン酸アミド、マレイン酸イミドなどが挙げられる。前記 (al)〜（a4)で表される 重合体を不飽和カルボン酸またはその誘導体により変性する方法としては、例えば、 有機過酸化物などのラジカル発生剤の存在下、あるいは紫外線や放射線の存在下 に不飽和カルボン酸またはその誘導体を前記 (al)〜（a4)で表される（共)重合体と 反応させる方法などが挙げられる。  In the modified polyolefin (a5), examples of the unsaturated carboxylic acid or derivative thereof include maleic acid, maleic anhydride, maleic ester, maleic halide, maleic amide, maleic imide and the like. . Examples of a method for modifying the polymer represented by (al) to (a4) with an unsaturated carboxylic acid or a derivative thereof include, for example, the presence of a radical generator such as an organic peroxide, or the presence of ultraviolet rays or radiation. Examples thereof include a method in which an unsaturated carboxylic acid or a derivative thereof is reacted with the (co) polymer represented by the above (al) to (a4).
[0086] (al)〜（a5)力 なる群力 選ばれるポリオレフイン (a")を製造する条件や方法に ついては特に制限はないが、例えばチーグラー 'ナッタ触媒やメタ口セン触媒、ポスト メタ口セン触媒などの公知の遷移金属触媒を用いた配位ァ-オン重合や、高圧下あ るいは放射線照射下でのラジカル重合などの方法を用いることができる。また、上記 方法で製造したポリオレフインを熱やラジカルで分解したものを用いることもできる。  [0086] (al) to (a5) force group force There are no particular restrictions on the conditions and method for producing the selected polyolefin (a "). For example, Ziegler 'Natta catalyst, A method such as coordination ion polymerization using a known transition metal catalyst such as a catalyst, radical polymerization under high pressure or irradiation, etc. can be used. Or those decomposed by radicals can also be used.
[0087] なお、ブロック（a)は、上述のように炭素 炭素二重結合を一つだけ有するモノォレ フィンィ匕合物あるいは、芳香環を有するモノォレフィンィ匕合物力も構成されて!、ること が必要であり、炭素 炭素二重結合を複数有する化合物、例えばへキサジェンゃォ クタジェンなどの直鎖状ジェン化合物、ジビュルベンゼンなどのスチレン系ジェンィ匕 合物、ビュルノルボルネンゃェチリデンノルボルネンなどの環状ジォレフイン化合物 などを上記 α—才レフインと共重合して得られる重合体を用いた場合、後述するハロ ゲンィ匕の段階でジェンィ匕合物に由来する不飽和結合同士が架橋してゲルイ匕するた め好ましくない。したがってハロゲンィ匕させるポリオレフイン (a")として、上記のような（ al)〜（a5)力 なる群力 選ばれるポリオレフインが用いられ、これらは 2種以上組み 合わせて用いられてもよい。  [0087] It should be noted that the block (a) needs to have a monoolefin-compound compound having only one carbon-carbon double bond as described above or a mono-olefin compound compound having an aromatic ring! A compound having a plurality of carbon-carbon double bonds, for example, a linear gen compound such as hexagen octagen, a styrene-based gen compound such as dibylbenzene, or a cyclic diolefin such as burnorbornene or ethylidene norbornene. In the case of using a polymer obtained by copolymerizing a compound or the like with the α-year-old refin, unsaturated bonds derived from the Geny compound are cross-linked and gelled at the stage of the halogeni described below. It is not preferable. Therefore, as the polyolefin to be halogenated (a "), the polyolefin selected from the group forces (al) to (a5) as described above is used, and these may be used in combination of two or more.
[0088] 《ハロゲン変性ポリオレフイン（a，）》 ハロゲン変性ポリオレフイン（a，）は、上記のようなポリオレフイン（a，，）をハロゲン化さ せることによって製造することができる。このようにして得られたハロゲン変性ポリオレ フィン（a，）のハロゲン含有率は、 0. 01〜70重量0 /0、好ましくは 0. 02〜50重量0 /0、 さらに好ましくは 0. 05〜30重量％である。このようなハロゲンは、フッ素、塩素、臭素 またはヨウ素力 選ばれ、これらの組み合わせであってもよい。 [0088] << Halogen-modified polyolefin (a,) >> The halogen-modified polyolefin (a,) can be produced by halogenating the above-described polyolefin (a,). Halogen content of thus obtained halogen-modified Poriore fin (a,) is from 0.01 to 70 weight 0/0, preferably from 0.02 to 50 weight 0/0, more preferably 0. 05～ 30% by weight. Such a halogen is selected from fluorine, chlorine, bromine or iodine, and may be a combination thereof.
[0089] またハロゲン変性ポリオレフイン (a' )は、重合体主鎖の末端に下記一般式 (I)〜（III )で表される構成単位力 選ばれる少なくとも一つの構成単位が接続された構造、お よび Zまたは重合体主鎖中に下記一般式 (IV)〜 (VII)で表される構成単位から選ば れる少なくとも一つの構成単位が挿入された構造を有する。  [0089] The halogen-modified polyolefin (a ') has a structure in which at least one structural unit selected from structural unit forces represented by the following general formulas (I) to (III) is connected to the terminal of the polymer main chain: And at least one constitutional unit selected from constitutional units represented by the following general formulas (IV) to (VII) in Z or the polymer main chain.
[0090] [化 5]  [0090] [Chemical 5]
Figure imgf000019_0001
Figure imgf000019_0001
、3a, 3a
[0091] 上記一般式 (I)〜 (VII)にお 、て、 Xはハロゲン原子を表し、 Rla、 Rlb、 R2 R2b、 R3 、 R3b、 R3e、 R½、 R5a、 R5b、 R6a、 R6b、 R7a、 R7bは水素原子、ハロゲン原子、一つ以上の ハロゲン原子で置換されて 、てもよ 、炭化水素基、酸素含有基または窒素含有基を 表し、互いに同一でも異なっていてもよい。 In the above general formulas (I) to (VII), X represents a halogen atom, and R la , R lb , R 2 R 2b , R 3 , R 3b , R 3e , R ½ , R 5a , R 5b , R 6a , R 6b , R 7a , R 7b may be substituted with a hydrogen atom, a halogen atom, or one or more halogen atoms, and may represent a hydrocarbon group, an oxygen-containing group, or a nitrogen-containing group These may be the same as or different from each other.
ノ、ロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、好ましくは塩素または 臭素である。  Examples of the hydrogen atom and the rogen atom include fluorine, chlorine, bromine and iodine, preferably chlorine or bromine.
[0092] 炭化水素基として具体的には、メチル、ェチル、 n—プロピル、イソプロピル、 n—ブ チル、イソブチル、 sec-ブチノレ、 tert-ブチル、ネオペンチル、 n—へキシルなどの炭 素原子数 1〜30、好ましくは 1〜20の直鎖状または分岐状のアルキル基、ビュル、ァ リル、イソプロべ-ルなどの炭素原子数 2〜30、好ましくは 2〜20の直鎖状または分 岐状のアルケ-ル基、ェチニル、プロパルギルなど炭素原子数 2〜30、好ましくは 2 〜20の直鎖状または分岐状のアルキ-ル基、フエ-ル、ベンジル、ナフチル、ビフエ -ル、ターフェ-ル、フエナントリル、アントラセ-ルなどの炭素原子数 6〜30、好まし くは 6〜20のァリール基、トリル、 iso-プロピルフエ-ル、 tert-ブチルフエ-ル、ジメチ ルフエニル、ジー t—ブチルフエ-ルなどのアルキル置換ァリール基などが挙げられ る。上記炭化水素基は、水素原子がハロゲンで置換されていてもよぐたとえば、トリ フルォロメチル、ペンタフルォロフエ-ル、クロ口フエ-ルなどの炭素原子数 1〜30、 好ましくは 1〜20のハロゲンィ匕炭化水素基が挙げられる。また、上記炭化水素基は、 他の炭化水素基で置換されていてもよぐたとえば、ベンジル、タミルなどのァリール 基置換アルキル基などが挙げられる。 [0092] Specific examples of the hydrocarbon group include carbons such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butinole, tert-butyl, neopentyl, and n-hexyl. A linear or branched alkyl group having 1 to 30 elemental atoms, preferably 1 to 20 carbon atoms, such as bur, aryl, isopropyl, etc., and a linear chain having 2 to 30, preferably 2 to 20 carbon atoms Or a branched or branched alkyl group such as branched alkyl group, ethynyl, propargyl, etc., having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, phenol, benzyl, naphthyl, biphenyl , Terfals, phenanthryls, anthraces, etc., 6-30 carbon atoms, preferably 6-20 aryl groups, tolyl, iso-propylphenol, tert-butylphenol, dimethylphenyl, di-t- And alkyl-substituted aryl groups such as butylphenol. The hydrocarbon group may have a hydrogen atom substituted with halogen. For example, the hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, black mouth Of the halogenated hydrocarbon group. The hydrocarbon group may be substituted with other hydrocarbon groups, for example, aryl group-substituted alkyl groups such as benzyl and Tamyl.
[0093] さらにまた、上記炭化水素基は、ヘテロ環式化合物残基、アルコキシ基、ァリーロキ シ基、エステル基、エーテル基、ァシル基、カルボキシル基、カルボナート基、ヒドロ キシ基、ペルォキシ基、カルボン酸無水物基などの酸素含有基、アミノ基、イミノ基、 アミド基、イミド基、ヒドラジノ基、ヒドラゾノ基、ニトロ基、ニトロソ基、シァノ基、イソシァ ノ基、シアン酸エステル基、アミジノ基、ジァゾ基、ァミノ基がアンモ-ゥム塩となったも のなどの窒素含有基などで置換されて 、てもよ!/、。  [0093] Furthermore, the hydrocarbon group includes a heterocyclic compound residue, an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic acid. Oxygen-containing groups such as anhydride groups, amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyanos groups, isocyanano groups, cyanate ester groups, amidino groups, diazo groups The amino group may be substituted with a nitrogen-containing group such as an ammonium salt!
[0094] これらのうち、特に、メチル、ェチル、 n—プロピル、イソプロピル、 n—ブチル、イソ ブチル、 sec-ブチル、 tert—ブチル、ネオペンチル、 n—へキシルなどの炭素原子数 1〜30、好ましくは 1〜20の直鎖状または分岐状のアルキル基、フエ-ル、ナフチル 、ビフエ-ル、ターフェ-ル、フエナントリル、アントラセ-ルなどの炭素原子数 6〜30 、好ましくは 6〜20のァリール基、これらのァリール基にハロゲン原子、炭素原子数 1 〜30、好ましくは 1〜20のアルキル基またはアルコキシ基、炭素原子数 6〜30、好ま しくは 6〜20のァリール基またはァリーロキシ基などの置換基が 1〜5個置換した置 換ァリール基などが好まし 、。 [0094] Among these, in particular, 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, etc. Is a linear or branched alkyl group having 1 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terfal, phenanthryl, anthracyl, etc., preferably 6 to 20 carbon atoms. Groups, these aryl groups such as halogen atoms, alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, aryl groups or aryloxy groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, etc. Preferred is a substituted aryl group in which 1 to 5 substituents are substituted.
[0095] 酸素含有基は、基中に酸素原子を 1〜5個含有する基であり、具体的には、例えば アルコキシ基、ァリーロキシ基、エステル基、エーテル基、ァシル基、カルボキシル基 、カルボナート基、ヒドロキシル基、ペルォキシ基、カルボン酸無水物基などが挙げら れ、アルコキシ基、ァリーロキシ基、ァセトキシ基、カルボニル基、ヒドロキシル基など が好ましい。なお酸素含有基が炭素原子を含む場合は、炭素原子数 1〜30、好まし くは 1〜20の範囲にあることが望ましい。これらの酸素含有基のうち、アルコキシ基と しては、メトキシ、エトキシ、 n-プロポキシ、イソプロポキシ、 n—ブトキシ、イソブトキシ、 tert-ブトキシなどが、ァリーロキシ基としては、フエノキシ、 2, 6—ジメチルフエノキシ、 2,4,6—トリメチルフエノキシなど力 ァシル基としては、ホルミル、ァセチル、ベンゾィ ル、 p—クロ口べンゾィル、 p—メトキシベンソィルなど力 エステル基としては、ァセチ ルォキシ、ベンゾィルォキシ、メトキシカルボニル、フエノキシカルボニル、 p—クロロフ エノキシカルボニルなどが好ましく例示される。 [0095] The oxygen-containing group is a group containing 1 to 5 oxygen atoms in the group. Specifically, for example, an alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group A carbonate group, a hydroxyl group, a peroxy group, a carboxylic acid anhydride group and the like, and an alkoxy group, an aryloxy group, an acetoxy group, a carbonyl group, a hydroxyl group and the like are preferable. When the oxygen-containing group contains a carbon atom, the number of carbon atoms is preferably 1 to 30, and more preferably 1 to 20. Among these oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc., and aryloxy groups include phenoxy, 2,6-dimethyl. Phenoxy, 2,4,6-trimethylphenoxy and other strong acyl groups include formyl, acetyl, benzoyl, p-chlorobenzoyl, p-methoxybenzol and other ester groups such as acetyloxy Benzyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like are preferably exemplified.
[0096] 窒素含有基は、基中に窒素原子を 1〜5個含有する基であり、具体的には、例えば アミノ基、イミノ基、アミド基、イミド基、ヒドラジノ基、ヒドラゾノ基、ニトロ基、ニトロソ基、 シァノ基、イソシァノ基、シアン酸エステル基、アミジノ基、ジァゾ基、ァミノ基がアンモ -ゥム塩となったものなどが挙げられ、アミノ基、イミノ基、アミド基、イミド基、ニトロ基、 シァノ基が好ましい。なお、窒素含有基が炭素原子を含む場合は、炭素原子数 1〜3 0、好ましくは 1〜20の範囲にあることが望ましい。これらの窒素含有基のうち、アミド 基としては、ァセトアミド、 N—メチルァセトアミド、 N—メチルベンズアミドなど力 アミ ノ基としては、メチルァミノ、ジメチルアミ入ジェチルアミ入ジプロピルアミ入ジブチ ルァミノ、ジシクロへキシルァミノなどのアルキルアミノ基；フエ-ルアミ入ジフエ-ル アミ入ジトリルアミ入ジナフチルァミノ、メチルフエ-ルァミノなどのァリールアミノ基ま たはアルキルァリールアミノ基など力 イミド基としては、ァセトイミド、ベンズイミドなど 力 イミノ基としては、メチルイミ入ェチルイミ入プロピルイミ入ブチルイミ入フエ- ルイミノなどが好ましく例示される。  [0096] The nitrogen-containing group is a group containing 1 to 5 nitrogen atoms in the group. Specifically, for example, an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group , Nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, those in which the amino group has become an ammonium salt, and the like, such as amino group, imino group, amide group, imide group, A nitro group and a cyano group are preferred. When the nitrogen-containing group contains a carbon atom, it is desirable that the number of carbon atoms is 1 to 30 and preferably 1 to 20. Among these nitrogen-containing groups, the amide group includes acetamide, N-methylacetamide, N-methylbenzamide, and the like. Examples of the force-containing amino group include methylamino, dimethylamino-containing dimethylamino-containing dipropylamino-containing dibutylamino, and dicyclohexylamino. Alkylamino group: Phenylamine-containing diphenyl Ami-filled Ditolylamin-filled dinaphthylamino, methylphenylamino, etc. Arylamino group or alkylarylamino group, etc. Preferable examples include cetylimi-containing propylimi-containing butylimi-containing leumino.
[0097] 以下に、上記一般式 (I)〜 (VII)で表される構成単位の好ま 、形態にっ 、て構造 式で例示する。  [0097] In the following, structural units are exemplified according to the preferred and forms of the structural units represented by the general formulas (I) to (VII).
[0098] [化 6] [上記一般式 （ I ) で表される構成単位の好ましい形態の例示] [0098] [Chemical 6] [Example of preferred form of structural unit represented by general formula (I) above]
Figure imgf000022_0001
Figure imgf000022_0001
上式中、 Xはハロゲン原子を表す。  In the above formula, X represents a halogen atom.
[0099] [化 7]  [0099] [Chemical 7]
[上記一般式 （II) で表される構成単位の好ましい形態の例示]  [Examples of preferred forms of structural units represented by general formula (II) above]
CH3
Figure imgf000022_0002
CH 3
Figure imgf000022_0002
上式中、 Xはハロゲン原子を表す。  In the above formula, X represents a halogen atom.
[0100] [化 8] [0100] [Chemical 8]
[上記一般式 （III) で表される構成単位の好ましい形態の例示]  [Examples of preferred forms of structural units represented by general formula (III) above]
Figure imgf000022_0003
Figure imgf000022_0003
上式中、 Xはハロゲン原子を表す。 [0101] [化 9] In the above formula, X represents a halogen atom. [0101] [Chemical 9]
[上記一般式 （IV) で表される構成単位の好ましい形態の例示]
Figure imgf000023_0001
[Examples of preferred forms of the structural unit represented by the general formula (IV)]
Figure imgf000023_0001
上式中、 Xはハロゲン原子を表す。  In the above formula, X represents a halogen atom.
[化 10]  [Chemical 10]
[上記一般式 （V) で表される構成単位の好ましい形態の例示]  [Example of preferred form of structural unit represented by general formula (V) above]
Figure imgf000023_0002
Figure imgf000023_0002
上式中、 Xはハロゲン原子を表す。  In the above formula, X represents a halogen atom.
[0103] [化 11]  [0103] [Chemical 11]
[上記一般式 （V I ) で表される構成単位の好ましい形態の例示][Example of preferred form of structural unit represented by general formula (V I) above]
H3
Figure imgf000023_0003
上式中、 Xはハロゲン原子を表す。 H 3
Figure imgf000023_0003
In the above formula, X represents a halogen atom.
[0104] [化 12] [上記一般式 で表される構成単位の好ましい形態の例示] [0104] [Chemical 12] [Examples of preferred forms of the structural unit represented by the general formula]
Figure imgf000024_0001
Figure imgf000024_0001
上式中、 Xはハロゲン原子を表す。  In the above formula, X represents a halogen atom.
[0105] またハロゲン変性ポリオレフイン (a' )は、重合体主鎖の末端に上記一般式 (I)〜（III )で表される構成単位中の炭素 炭素二重結合に水素原子 2個が付加して炭素 炭素単結合になった構造として表される構成単位力 選ばれる少なくとも一つの構 成単位が接続された構造、および Zまたは重合体主鎖中に下記一般式 (IV)〜 (VII) で表される構成単位中の炭素 炭素二重結合に水素原子 2個が付加して炭素 炭 素単結合になった構造として表される構成単位カゝら選ばれる少なくとも一つの構成 単位が挿入された構造を有することもある。そのような構成単位の好ま ヽ形態につ いて以下に構造式で示す。  [0105] In the halogen-modified polyolefin (a '), two hydrogen atoms are added to the carbon-carbon double bond in the structural unit represented by the above general formulas (I) to (III) at the end of the polymer main chain. The structural unit force expressed as a carbon-carbon single bond is a structure in which at least one selected structural unit is connected, and the following general formulas (IV) to (VII) in Z or the polymer main chain: At least one structural unit selected from a structural unit represented by a structure in which two hydrogen atoms are added to a carbon-carbon double bond to form a carbon-carbon single bond in the structural unit represented by May have a different structure. The preferred form of such a structural unit is shown below in the structural formula.
[0106] [化 13] [0106] [Chemical 13]
Figure imgf000025_0001
Figure imgf000025_0001
CH3 CH3 CH 3 CH 3
X  X
\ ,CH2、 \ H2 X CH \, CH 2 , \ H 2 X CH
CH2 CH CH2 z 、CH' CH2 CH CH 2 z, CH '
X X X X
X X X X X X
Figure imgf000025_0002
Figure imgf000025_0002
Xはハロゲン原子を示す。  X represents a halogen atom.
ここで、重合体主鎖とは、重合体一分子鎖中に存在する aーォレフインおよびそれ と共重合させたコモノマーに由来する繰り返し単位が最も多い、すなわちモノマー連 鎖構造の最も長い部分を表し、そのような重合体主鎖には 2つの末端位置が存在す る。したがって重合体主鎖の末端に上記一般式 (I)〜 (III)で表される構成単位およ びその構成単位中に含まれる炭素 炭素二重結合に水素原子 2個が付加して炭素 炭素単結合になった構造として表される構成単位力 選ばれる少なくとも一つの 構成単位が接続されている場合、重合体一分子鎖中に含まれる上記構成単位の個 数は最大で 2個となる。また、重合体主鎖中に下記一般式 (IV)〜 (VII)で表される構 成単位およびその構成単位中に含まれる炭素 炭素二重結合に水素原子 2個が付 カロして炭素一炭素単結合になった構造として表される構成単位力 選ばれる少なくと も一つの構成単位が挿入されている場合、その重合体一分子鎖当たりに存在する上 記構成単位の個数に関しては特に制限はないが、個数が多すぎるとポリオレフインと しての性質が充分に発現しない可能性がある。したがって、上記一般式 (I)〜(VII) で表される構成単位および上記一般式 (I)〜 (VII)で表される構成単位中に含まれる 炭素 炭素二重結合に水素原子 2個が付加して炭素 炭素単結合になった構造と して表される構成単位を合計した全構成単位の総数としては、ハロゲン原子含有量 に換算して 0. 01〜70重量％であることが好ましぐ 0. 05〜50重量％であることがよ り好ましい。また、一つの重合体分子鎖中にこれらの構成単位が数種類含まれてい てもよい。これらの構成単位のうち、炭素 炭素二重結合が存在し、さらにそのァリル 位にハロゲン原子が付加した構造を有する上記一般式 (I)〜 (νπ)で表される構成単 位を含むハロゲン変性ポリオレフイン (a' )は、従来公知の塩素化ポリエチレン、塩素 化ポリプロピレンなどと同様にハロゲンィ匕ポリオレフインとして接着剤や塗料用榭脂の 用途に利用できるだけでなぐ分子内に存在する炭素 炭素二重結合の反応性を 生力してハロゲン以外の官能基を導入したり、グラフトポリマー製造用のマクロモノマ 一として用いたりすることができる。 Here, the polymer main chain represents the longest part of the monomer chain structure having the largest number of repeating units derived from a-olefin and the comonomer copolymerized therewith in one polymer molecular chain, There are two terminal positions in such a polymer backbone. Therefore, two hydrogen atoms are added to the structural unit represented by the above general formulas (I) to (III) and the carbon-carbon double bond contained in the structural unit at the end of the polymer main chain to form a carbon Structural unit force expressed as a bonded structure When at least one selected structural unit is connected, the maximum number of the structural units contained in one polymer molecular chain is two. In addition, the structural unit represented by the following general formulas (IV) to (VII) in the polymer main chain and the carbon-carbon double bond contained in the structural unit are attached with two hydrogen atoms to form a carbon atom. Structural unit force expressed as a structure with a single carbon bond When at least one selected structural unit is inserted, there is a particular restriction on the number of structural units present per molecular chain of the polymer. There is no, but too many and polyolefin This property may not be fully developed. Therefore, two hydrogen atoms are present in the carbon-carbon double bond contained in the structural units represented by the general formulas (I) to (VII) and the structural units represented by the general formulas (I) to (VII). The total number of all structural units, which are the total of the structural units represented as carbon-carbon single bonds added, is preferably 0.01 to 70% by weight in terms of halogen atom content. It is more preferably 0.05 to 50% by weight. Further, several kinds of these structural units may be contained in one polymer molecular chain. Among these structural units, halogen-modified products containing structural units represented by the above general formulas (I) to (νπ) having a structure in which a carbon-carbon double bond is present and a halogen atom is added to the aryl position. Polyolefin (a ') is a carbon-carbon double bond existing in a molecule that can only be used as a halogenated polyolefin for use in adhesives and coating resin as well as the conventionally known chlorinated polyethylene and chlorinated polypropylene. Functionality other than halogen can be introduced by virtue of reactivity, or it can be used as a macromonomer for producing graft polymers.
ノ、ロゲン変性ポリオレフイン (a' )中に存在するハロゲン原子含有量は、例えば元素 分析やイオンクロマトグラフィーなどの方法により測定することができ、測定値は通常 、重量％単位で表される。また、ハロゲン変性ポリオレフイン (a' )中に存在する炭素 炭素二重結合含有量は、例えば赤外分光法や核磁気共鳴法 (NMR)などの方法 により測定することができ、測定値は通常、重量％あるいはモル％単位で表される。 さらに、炭素 炭素二重結合のァリル位に存在するハロゲン原子については、例え ば NMRにより確認および定量することができる。ァリル位に存在するハロゲン原子確 認の具体例としては、例えば上記方法で得られた臭素化ポリプロピレンの重水素化 オルトジクロロベンゼンを溶媒に用いたプロトン NMRにおいて、炭素 炭素二重結 合に基づくシグナルは通常 δ 4. 5〜6. Oppmの範囲に観測され、臭素原子が結合 したァリル位のメチレン基およびメチン基は通常 δ 3. 5〜4. 5ppmに観測される。ァ リル位以外のメチレン基およびメチン基に臭素原子が導入された場合のシグナル位 置は通常、 S 3. 0〜3. 5ppmであるため、臭素原子がァリル位に存在しているかそう でないかは容易に識別可能である。加えて、例えばプロトン プロトン二次元 NMR( HH— COSY)を用いることにより、上記炭素—炭素二重結合に基づくシグナルと、 臭素原子が結合したメチレン基およびメチン基のシグナルとの相関関係を確認する ことも可能である。一方、ハロゲン変性ポリオレフイン (a' )の分子量は、例えばゲルパ 一ミエーシヨンクロマトグラフィー（GPC)により測定することができ、そのようにして測 定された数平均分子量 (Mn)の値とハロゲン変性ポリオレフイン (a' )中に含まれる各 ユニット（各ォレフインモノマーに由来するユニット、ハロゲンが結合したユニット、炭 素 炭素二重結合ユニットなど）の組成比 (モル分率)から、炭素 炭素二重結合の 含有量を一分子鎖あたりの平均値として算出することができる。ハロゲンが結合した ユニットの一分子鎖あたりの平均値力 ォレフィン系ブロックポリマー（A2)中のブロッ ク (a)に結合したブロック (b)の一分子鎖当たり結合個数をとなる。本発明において、 ォレフィン系ブロックポリマー（A2)は、ブロック（b)がブロック（a)—分子鎖当たり 0. 5 〜5個結合しており、好ましくは 0. 5〜3. 5個結合しており、より好ましくは 0. 5〜3個 結合している。ブロック (a)に結合したブロック (b)の一分子鎖当たり結合個数力この 範囲から外れると、ォレフィン系ブロックポリマー (A2)がポリオレフイン (A1)と榭脂（ B)の界面に分布しにくくなり、したがって、界面がはく離しやすくなり機械的強度が低 下する。 The halogen atom content present in the rogen-modified polyolefin (a ′) can be measured, for example, by a method such as elemental analysis or ion chromatography, and the measured value is usually expressed in units of% by weight. The carbon-carbon double bond content present in the halogen-modified polyolefin (a ′) can be measured by methods such as infrared spectroscopy and nuclear magnetic resonance (NMR), and the measured value is usually Expressed in units of wt% or mol%. Furthermore, the halogen atom present at the aryl position of the carbon-carbon double bond can be confirmed and quantified by, for example, NMR. Specific examples of the confirmation of the halogen atom present at the aryl position include, for example, a signal based on a carbon-carbon double bond in proton NMR using deuterated orthodichlorobenzene as a solvent for the brominated polypropylene obtained by the above method. Is usually observed in the range of δ 4.5 to 6. Oppm, and the methylene group and methine group at the aryl position to which a bromine atom is bonded are usually observed in the range of δ 3.5 to 4.5 ppm. When a bromine atom is introduced into a methylene group and a methine group other than the aryl position, the signal position is usually S 3.0 to 3.5 ppm, so whether the bromine atom is present in the aryl position or not. Are easily identifiable. In addition, for example, by using proton proton two-dimensional NMR (HH—COZY), the signal based on the carbon-carbon double bond, It is also possible to confirm the correlation with the signals of the methylene group and methine group to which the bromine atom is bonded. On the other hand, the molecular weight of halogen-modified polyolefin (a ′) can be measured, for example, by gel permeation chromatography (GPC). The value of the number average molecular weight (Mn) thus measured and the halogen-modified polyolefin From the composition ratio (molar fraction) of each unit (unit derived from each olefin monomer, unit bonded with halogen, carbon-carbon double bond unit, etc.) contained in the polyolefin (a '), carbon The content of heavy bonds can be calculated as an average value per molecular chain. The average force per molecular chain of the unit to which the halogen is bonded is the number of bonds per molecular chain of the block (b) bonded to the block (a) in the olefin block polymer (A2). In the present invention, the olefin-based block polymer (A2) has 0.5 to 5 blocks (b) bonded to the block (a) -molecular chain, preferably 0.5 to 3.5 bonded to the block (b). More preferably, 0.5 to 3 are bonded. If the number of bonds per molecular chain of the block (b) bonded to the block (a) is outside this range, the olefin-based block polymer (A2) will not easily be distributed at the interface between the polyolefin (A1) and the resin (B). Therefore, the interface is easily peeled off and the mechanical strength is lowered.
[0109] 《ハロゲン変性ポリオレフイン（a，）の製造方法》  [0109] <Method for producing halogen-modified polyolefin (a,)>
ハロゲン変性ポリオレフイン（a，）は、前述のポリオレフイン（a，，）とハロゲン化剤とを 反応させることにより製造される。  The halogen-modified polyolefin (a,) is produced by reacting the aforementioned polyolefin (a ,,) with a halogenating agent.
[0110] ハロゲン化剤としては、ポリオレフイン（a，，）をハロゲン化してハロゲン変性ポリオレフ イン (Α' )を製造できるものであれば特に制限はないが、具体的には、塩素分子、臭 素分子、ヨウ素分子、三塩化リン、三臭化リン、三ヨウ化リン、五塩化リン、五臭化リン 、五ョウイ匕リン、塩化チォ -ル、塩化スルフリル、臭化チォニル、 Ν—クロロスクシンィ ミド、 Ν ブロモスクシンイミド、 Ν ブロモカプロラタタム、 Ν ブロモフタルイミド、 1,3 ジブ口モー 5,5—ジメチルヒダントイン、 Ν—クロログルタルイミド、 Ν ブロモグルタ ルイミド、 Ν,Ν'—ジブ口モイソシァヌル酸、 Ν ブロモアセトアミド、 Ν ブロモカルバ ミド酸エステル、ジォキサンジブ口ミド、フエ-ルトリメチルアンモ-ゥムトリブ口ミド、ピリ ジ-ゥムヒドロブロミドペルブロミド、ピロリドンヒドロトリブ口ミド、次亜塩素酸 t ブチル 、次亜臭素酸 t—プチル、塩化銅 (II)、臭化銅 (II)、塩ィ匕鉄 (III)、塩ィ匕ォキサリル、 IB rなどが挙げられる。これらのうち、好ましくは塩素分子、臭素分子、 N クロロスクシン イミド、 N ブロモスクシンイミド、 N ブロモカプロラタタム、 N ブロモフタルイミド、 1 ,3—ジブ口モー 5,5—ジメチルヒダントイン、 N—クロログルタルイミド、 N ブロモグル タルイミド、 Ν,Ν' ジブ口モイソシァヌル酸であり、より好ましくは臭素、 Ν ブロモス クシンイミド、 Ν ブロモカプロラタタム、 Ν ブロモフタルイミド、 1,3 ジブ口モー 5,5 ージメチルヒダントイン、 Ν ブロモグルタルイミド、 Ν,Ν'—ジブ口モイソシァヌル酸な どの Ν— Br結合を有する化合物である。 [0110] The halogenating agent is not particularly limited as long as it can halogenate polyolefin (a ,,) to produce halogen-modified polyolefin (Α '). Molecule, iodine molecule, phosphorous trichloride, phosphorous tribromide, phosphorous triiodide, phosphorous pentachloride, phosphorous pentabromide, pentaphosphorus, thiol chloride, sulfuryl chloride, thionyl bromide, ク ロ ロ -chlorosuccinimide, Ν Bromosuccinimide, ブ ロ モ Bromocaprolatatam, Ν Bromophthalimide, 1,3 Jib mouth mo 5,5-Dimethylhydantoin, Ν-Chloroglutarimide, ブ ロ モ Bromoglutarimide, Ν, Ν'-Dibu mouth moisocyanuric acid, ブ ロ モ Bromoacetamide , Ν Bromocarbamic acid ester, Dioxanedibu mouth amide, Phenol trimethyl ammonium tribuamide, Pyridilum hydrobromide Doperbromide, pyrrolidone hydrotrib mouthamide, t-butyl hypochlorite, t-butyl hypobromite, copper (II) chloride, copper (II) bromide, salt iron (III), salt oxalyl, IB r. Among these, preferably chlorine molecule, bromine molecule, N chlorosuccinimide, N bromosuccinimide, N bromocaprolatatam, N bromophthalimide, 1,3-dib-mouthed 5,5-dimethylhydantoin, N-chloroglutarimide, N Bromoglutarimide, Ν, Ν 'Dib mouth moisocyanuric acid, more preferably bromine, ブ ロ モ Bromosuccinimide, Ν Bromocaprolatatam, Ν Bromophthalimide, 1,3 Dib mouth moe 5,5-dimethylhydantoin, Ν Bromoglutar It is a compound having a Br-Br bond such as imide, Ν, Ν'-jib mouth moisocyanuric acid.
ポリオレフイン (a")とハロゲン化剤との反応は、不活性ガス雰囲気下で行うことが好 ましい。不活性ガスとしては、例えば窒素、ァノレゴン、ヘリウムなどの不活性ガスが挙 げられる。また、本発明の反応には、必要に応じて溶媒を使用することができる。溶 媒としては反応を阻害しな 、ものであれば何れでも使用することができるが、例えば、 具体例として、ベンゼン、トルエンおよびキシレン等の芳香族炭化水素系溶媒、ペン タン、へキサン、ヘプタン、オクタン、ノナンおよびデカン等の脂肪族炭化水素系溶媒 、シクロへキサン、メチルシクロへキサンおよびデカヒドロナフタレンのような脂環式炭 ィ匕水素系溶媒、クロ口ベンゼン、ジクロロベンゼン、トリクロ口ベンゼン、塩化メチレン、 クロ口ホルム、四塩ィ匕炭素およびテトラクロロエチレン、テトラクロロェタン等の塩素化 炭化水素系溶媒、メタノール、エタノール、 n—プロパノール、 iso プロパノール、 n ーブタノール、 sec ブタノールおよび tert ブタノール等のアルコール系溶媒、ァセ トン、メチルェチルケトンおよびメチルイソブチルケトン等のケトン系溶媒；酢酸ェチル およびジメチルフタレート等のエステル系溶媒、ジメチルエーテル、ジェチルエーテ ル、ジ n—ァミルエーテル、テトラヒドロフランおよびジォキシァ-ソールのようなェ 一テル系溶媒等を挙げることができる。好ましくは、ペンタン、へキサン、ヘプタン、ォ クタン、ノナンおよびデカン等の脂肪族炭化水素系溶媒、シクロへキサン、メチルシク 口へキサンおよびデカヒドロナフタレンのような脂環式炭化水素系溶媒、クロ口べンゼ ン、ジクロロベンゼン、トリクロ口ベンゼン、塩化メチレン、クロ口ホルム、四塩化炭素お よびテトラクロロエチレン、テトラクロロェタン等の塩素化炭化水素系溶媒が挙げられ る。これらの溶媒は、単独でもまたは 2種以上を混合して使用してもよい。また、これら の溶媒の使用によって、反応液が均一相となることが好ましいが、不均一な複数の相 となっても構わない。 The reaction between the polyolefin (a ") and the halogenating agent is preferably carried out in an inert gas atmosphere. Examples of the inert gas include inert gases such as nitrogen, anoregone, and helium. In the reaction of the present invention, a solvent can be used as necessary, and any solvent can be used as long as it does not inhibit the reaction. , Aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, fats such as cyclohexane, methylcyclohexane and decahydronaphthalene Cyclic hydrocarbons, hydrogenated solvents, black benzene, dichlorobenzene, trichloro benzene, methylene chloride, black chloroform, tetrasalt carbon, and Chlorinated hydrocarbon solvents such as trachloroethylene and tetrachloroethane, methanol solvents, ethanol, n-propanol, isopropanol, n-butanol, sec butanol and tert butanol alcohol solvents such as acetone and methyl ethyl ketone And ketone solvents such as methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; ether solvents such as dimethyl ether, jetyl ether, di-n-amyl ether, tetrahydrofuran, and dioxy-sol. Preferably, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, chlorine mouth And chlorinated hydrocarbon solvents such as benzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, tetrachloroethane, etc. These solvents can be used alone or in combination. In addition, it is preferable that the reaction solution becomes a homogeneous phase by using these solvents, but a plurality of heterogeneous phases may be used. It doesn't matter.
[0112] ハロゲン化剤との反応においては、反応を促進するために必要に応じてラジカル開 始剤を添加することもできる。ラジカル開始剤としては、例えば、ァゾビスイソプチ口- トリル、ァゾビス 2,4 ジメチルバレロニトリル、ァゾビスシクロへキサンカルボ二トリ ル、ァゾビス 2—アミジノプロパン塩酸塩、ァゾビスイソ酪酸ジメチル、ァゾビスイソ ブチルアミジン塩酸塩または 4,4' ァゾビスー4 シァノ吉草酸等のァゾ系開始剤、 過酸化べンゾィル、 2,4 ジクロル過酸化べンゾィル、過酸化ジー tert ブチル、過 酸化ラウロイル、過酸化ァセチル、過酸化ジイソプロピルジカーボネート、タメンヒドロ ペルォキシド、 tert ブチルヒドロペルォキシド、ジクミルペルォキシド、 p—メンタンヒ ドロペルォキシド、ピナンヒドロペルォキシド、メチルェチルケトンペルォキシド、シクロ へキサノンペルォキシド、ジイソプロピルペルォキシジカルボナート、 tert—ブチルぺ ルォキシラウレート、ジー tert ブチルペルォキシフタレート、ジベンジルォキシドまた は 2, 5 ジメチルへキサン 2, 5 ジヒドロペルォキシド等の過酸ィ匕物系開始剤、ま たは過酸化ベンゾィル Ν,Ν ジメチルァユリンまたはペルォキソ二硫酸 亜硫酸 水素ナトリウム等のレドックス系開始剤等が挙げられる。これらのうち、ァゾ系開始剤ま たは過酸ィ匕物系開始剤が好ましぐ更に好ましくは、過酸化べンゾィル、過酸化ジー t ert ブチル、過酸化ラウロイル、過酸化ァセチル、過酸化ジイソプロピルジカーボネ ート、タメンヒドロペルォキシド、 tert ブチルヒドロペルォキシド、ジクミルペルォキシ ド、ァゾビスイソブチロニトリル、ァゾビス 2,4 ジメチルバレロニトリル、ァゾビスシク 口へキサンカルボ-トリル、ァゾビスイソ酪酸ジメチルである。これらのラジカル開始剤 は、単独でもまたは 2種以上を同時にまたは順次に使用することもできる。  [0112] In the reaction with the halogenating agent, a radical initiator may be added as necessary to accelerate the reaction. Radical initiators include, for example, azobisisoptyl-tolyl, azobis-2,4 dimethylvaleronitrile, azobiscyclohexanecarbonyl, azobis-2-amidinopropane hydrochloride, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, or 4,4 ′ Azobis-4 Sazovaleric acid and other azo initiators, benzoyl peroxide, 2,4 dichloroperoxybenzoic acid, tert-butyl peroxide, lauroyl peroxide, acetyl acetyl peroxide, diisopropyl dicarbonate, tamenhydroperoxide, tert butyl hydroperoxide, dicumyl peroxide, p-menthane hydroperoxide, pinane hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, tert- The Peroxyacid initiators such as ruperoxylaurate, di-tert-butylperoxyphthalate, dibenzyloxide or 2,5 dimethylhexane 2,5 dihydroperoxide, or peroxidation Examples include redox initiators such as benzoyl Ν, ジ メ チ ル dimethylaurine or peroxodisulfuric acid sodium hydrogen sulfite. Of these, azo initiators or peroxide initiators are preferable, and more preferable are benzoyl peroxide, tert-butyl peroxide, lauroyl peroxide, acetyl acetate, peroxide. Diisopropyl dicarbonate, tamen hydroperoxide, tert butyl hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, azobis 2,4 dimethylvaleronitrile, azobissic mouth hexanecarbo-tolyl Dimethyl azobisisobutyrate. These radical initiators can be used alone or in combination of two or more.
[0113] また、ポリオレフイン (a")とハロゲン化剤とを反応させる方法については、従来公知 の種々の方法が採用できる。例えば、ポリオレフイン (a")を溶媒に懸濁させ、あるい は溶解させて、通常— 80°C〜250°Cの温度、好ましくは室温以上溶媒の沸点以下 の温度で、ハロゲン化剤と必要に応じてラジカル開始剤などを添加混合して反応さ せる方法、あるいはポリオレフイン（a")をその融点以上、例えば、 180〜300°Cの温 度で溶融混練下にハロゲン化剤と必要に応じてラジカル開始剤とを接触させる方法 などが挙げられる。 以上の方法により、ハロゲン変性ポリオレフイン (a' )が製造される。 [0113] As a method of reacting polyolefin (a ") with a halogenating agent, various conventionally known methods can be employed. For example, polyolefin (a") is suspended in a solvent or dissolved. In general, a method of reacting by adding and mixing a halogenating agent and, if necessary, a radical initiator at a temperature of 80 ° C. to 250 ° C., preferably at a temperature of room temperature to the boiling point of the solvent, or Examples thereof include a method in which a polyolefin (a ") is brought into contact with a halogenating agent and, if necessary, a radical initiator while melting and kneading at a temperature equal to or higher than its melting point, for example, 180 to 300 ° C. The halogen-modified polyolefin (a ′) is produced by the above method.
[0114] <ブロック（b) > [0114] <Block (b)>
ォレフィン系ブロックポリマー（A2)を構成するブロック（b)の数平均分子量が 2,00 0〜200,000、好まし <は 5,000〜150,000の範囲である。数平均分子量力 00,00 0より高!、と、ポリオレフイン (A1)と榭脂（B)の界面にォレフィン系ブロックポリマー（A 2)が分布しにくくなり、したがって、界面がはく離しやすくなり機械的強度が低下する 。数平均分子量が 2,000より低いと、ポリオレフイン (A1)ゃ榭脂（B)と、ォレフィン系 ブロックポリマー (A2)との間での分子鎖同士のからみ合いが少なくなり、機械的強度 が低下する。  The number average molecular weight of the block (b) constituting the olefin-based block polymer (A2) is in the range of 2,000 to 200,000, preferably <5,000 to 150,000. The number-average molecular weight force is higher than 00,00 0 !, and the olefin-based block polymer (A 2) is less likely to be distributed at the interface between the polyolefin (A1) and the resin (B), and therefore the interface is easy to peel off. The mechanical strength decreases. When the number average molecular weight is lower than 2,000, the molecular chains become less entangled between polyolefin (A1) resin (B) and olefin-based block polymer (A2), and the mechanical strength is lowered.
[0115] ブロック（b)は、ラジカル重合性単量体力 選ばれる 1種以上のモノマーの単独重 合体または共重合体である。ラジカル重合性単量体としては、具体的には、  [0115] The block (b) is a homopolymer or copolymer of one or more monomers selected from radically polymerizable monomer forces. Specifically, as the radical polymerizable monomer,
(メタ)アクリル酸、（メタ)アクリル酸メチル、（メタ）アクリル酸ェチル、（メタ）アクリル酸 — n—プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸— n—ブチル、（メタ） アクリル酸イソブチル、（メタ）アクリル酸 tert ブチル、（メタ）アクリル酸 n—ペン チル、（メタ）アクリル酸— n—へキシル、（メタ）アクリル酸シクロへキシル、（メタ）アタリ ル酸—n—へプチル、（メタ）アクリル酸—n—ォクチル、（メタ）アクリル酸 2—ェチル へキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル 、（メタ）アクリル酸フ -ル、（メタ）アクリル酸トルィル、（メタ）アクリル酸ベンジル、（メ タ）アクリル酸一 2—メトキシェチル、（メタ）アクリル酸一 3—メトキシブチル、（メタ）ァク リル酸— 2—ヒドロキシェチル、（メタ）アクリル酸— 2—ヒドロキシプロピル、（メタ）アタリ ル酸ステアリル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸 2—アミノエチル、（メタ )アクリル酸 2— (ジメチルァミノ）ェチル、 y - (メタクリロイルォキシプロピル）トリメトキ シシラン、（メタ）アクリル酸のエチレンオキサイド付加物、（メタ）アクリル酸トリフルォロ メチルメチル、（メタ）アクリル酸 2—トリフルォロメチルェチル、（メタ）アクリル酸 2—パ 一フルォロェチルェチル、（メタ）アクリル酸 2—パーフルォロェチルー 2—パーフル ォロブチルェチル、（メタ）アクリル酸 2—パーフルォロェチル、（メタ）アクリル酸パー フルォロメチル、（メタ）アクリル酸ジパーフルォロメチルメチル、（メタ）アクリル酸 2— パーフルォロメチルー 2—パーフルォロェチルメチル、（メタ）アクリル酸 2—パーフル ォ口へキシルェチル、（メタ）アクリル酸 2—パーフルォロデシルェチル、（メタ）アタリ ル酸 2—パーフルォ口へキサデシルェチル等の（メタ）アクリル酸系モノマー、スチレ ン、ビュルトルエン、 a—メチルスチレン、クロルスチレン、スチレンスルホン酸及びそ の塩等のスチレン系モノマー、パーフノレオ口エチレン、パーフノレオ口プロピレン、フッ 化ビ-リデン等のフッ素含有ビュルモノマー、ビュルトリメトキシシラン、ビュルトリエト キシシラン等のケィ素含有ビュル系モノマー、無水マレイン酸、マレイン酸、マレイン 酸のモノアルキルエステル及びジアルキルエステル、フマル酸、フマル酸のモノアル キルエステルおよびジアルキルエステル、マレイミド、メチルマレイミド、ェチルマレイミ ド、プロピルマレイミド、ブチルマレイミド、へキシルマレイミド、ォクチルマレイミド、ド デシルマレイミド、ステアリルマレイミド、フエ-ルマレイミド、シクロへキシルマレイミド 等のマレイミド系モノマー、アクリロニトリル、メタタリ口-トリル等の-トリル基含有ビ- ル系モノマー、（メタ）アクリルアミド、 N メチル (メタ）アクリルアミド、 N ェチル (メタ） アクリルアミド、 N プロピル (メタ）アクリルアミド、 N—イソプロピル (メタ）アクリルアミド 、 N ブチル (メタ）アクリルアミド、 Ν,Ν ジメチル (メタ）アクリルアミド等のアミド基含 有ビュル系モノマー、酢酸ビュル、プロピオン酸ビュル、ピバリン酸ビュル、安息香酸 ビュル、桂皮酸ビュル等のビュルエステル系モノマー、エチレン、プロピレン、ブテン 等のォレフィン系モノマー、ブタジエン、イソプレン等のジェン系モノマー、塩化ビ- ル、塩ィ匕ビユリデン、塩化ァリル、ァリルアルコール等が挙げられる。これらの有機化 合物は、単独で、または 2種類以上を組み合わせて使用しても構わない。 (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid — n-propyl, isopropyl (meth) acrylate, (meth) acrylic acid — n-butyl, (meth) Isobutyl acrylate, tert butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) acrylic acid-n-hexyl, cyclohexyl (meth) acrylate, (meth) acrylate -Heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid 2-ethyl hexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic Acid furl, (meth) acrylic acid toluyl, (meth) acrylic acid benzyl, (meth) acrylic acid 1-methoxyethyl, (meth) acrylic acid 1-methoxybutyrate , (Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid 2-amino Ethyl, (meth) acrylic acid 2- (dimethylamino) ethyl, y- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylic acid, (meth) acrylic acid 2-Trifluoromethylethyl, (meth) acrylic acid 2-parfluoroethylethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid 2-par Fluoroethyl, perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate , (Meth) acrylate, 2-perfluoro full O b methyl-2-Per full O Roe chill methyl, (meth) acrylate, 2-Pafuru (Meth) acrylic monomers such as 2-hexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic acid 2-perfluorohexadecylethyl, styrene, butyltoluene, a — Styrene monomers such as methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof, fluorine-containing butyl monomers such as perfluoroethylene olefin, perfluoroolefin propylene, and vinylidene fluoride, carbylene such as butyltrimethoxysilane and butyltrioxysilane. Containing butyl monomers, maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, Maleimide monomers such as butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenolmaleimide, cyclohexylmaleimide, etc., and -tolyl group-containing vinyl monomers such as acrylonitrile and meta-tallowyl-tolyl, (Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, Ν, Ν dimethyl (meth) acrylamide, etc. Amide group-containing butyl monomers, butyl acetate, propionate, pivalate, benzoate, cinnamate and other olefin monomers such as ethylene, propylene and butene, butane Ene, diene monomers such as isoprene, bi chloride - le, Shioi匕 Biyuriden, Ariru chloride, § Lil alcohol. These organic compounds may be used alone or in combination of two or more.
ブロック (b)としては、（メタ）アクリル酸およびその誘導体、（メタ)アクリロニトリル、ス チレンおよびその誘導体、（メタ）アクリルアミドおよびその誘導体、マレイン酸および その誘導体、マレイミドおよびその誘導体、ビニルエステル類カゝら選ばれる一種ある いは二種以上の単量体を (共)重合して得られる重合体が好ましぐスチレン、アタリ 口-トリル、 2—ヒドロキシェチルメタタリレート、アクリル酸 n—ブチル、グリシジルメ タクリレートおよびメチルメタタリレートから選ばれる 1種あるいは 2種以上の単量体を（ 共)重合して得られる重合体がより好ましい。なお、榭脂 (B)としてポリカーボネート榭 脂 (bl)を用いる場合には、スチレン、アクリロニトリル、メチルメタタリレートから選ばれ る 1種あるいは 2種以上の単量体を (共)重合して得られる重合体が特に好ましく、榭 脂（B)としてアクリル系榭脂 (b2)を用いる場合には、メチルメタタリレートとが特に好 ましぐ榭脂（B)としてビュル重合体 (b3)を用いる場合には、（メタ)アクリル酸および その誘導体は 50mol%以下であることが特に好ましぐおよび榭脂 (B)としてポリフエ 二レンオキサイド (b4)を用いる場合にはスチレンが特に好ま 、。 Block (b) includes (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, (meth) acrylamide and derivatives thereof, maleic acid and derivatives thereof, maleimide and derivatives thereof, and vinyl esters. Among them, styrene, talari-tolyl, 2-hydroxyethyl methacrylate, and acrylic acid n- are preferred as polymers obtained by (co) polymerizing one or two or more monomers selected. A polymer obtained by (co) polymerizing one or two or more monomers selected from butyl, glycidyl methacrylate, and methyl methacrylate is more preferable. When the polycarbonate resin (bl) is used as the resin (B), it is obtained by (co) polymerizing one or more monomers selected from styrene, acrylonitrile, and methyl methacrylate. Particularly preferred polymers are When acrylic resin (b2) is used as the fat (B), methyl methacrylate is particularly preferred. When the bull polymer (b3) is used as the resin (B), (meth) acrylic is used. It is particularly preferred that the acid and its derivatives are not more than 50 mol%, and styrene is particularly preferred when using polyphenylene oxide (b4) as the resin (B).
[0117] ブロック (b)を構成する（共)重合体の溶解度パラメータ一はブロック (b)を構成する  [0117] The solubility parameter of the (co) polymer constituting block (b) constitutes block (b)
(共)重合体の組成力も計算できる。ブロック (b)の溶解度パラメータ一は 18〜25の 範囲であり、好ましくは 18. 2〜22の範囲であり、さらに好ましくは 18. 5〜20の範囲 である。なお、榭脂（B)がポリカーボネート (bl)である場合には、ブロック (b)の溶解 度パラメータ一は 18〜24の範囲であり、好ましくは 18. 5〜24の範囲であり、さらに 好ましくは 19〜24の範囲であることも望ましい。溶解度パラメーターの値力この範囲 から外れると、ブロック (b)と榭脂 (B)との相溶性が低下し、相容化剤としての効果が 低下、機械的強度が低下する。  The compositional power of the (co) polymer can also be calculated. The solubility parameter 1 of block (b) is in the range of 18-25, preferably in the range of 18.2-22, more preferably in the range of 18.5-20. When the resin (B) is polycarbonate (bl), the solubility parameter 1 of the block (b) is in the range of 18 to 24, preferably in the range of 18.5 to 24, and more preferably Is also preferably in the range of 19-24. If the value of the solubility parameter is out of this range, the compatibility between the block (b) and the resin (B) decreases, the effect as a compatibilizer decreases, and the mechanical strength decreases.
[0118] 共重合体の溶解度パラメータ一は、ブロック（b)の組成を Million Zillion softwa re, Inc.製 CHEOPS Ver. 4. 0に入力し、計算した。  [0118] The solubility parameter 1 of the copolymer was calculated by inputting the composition of the block (b) into CHEOPS Ver. 4.0 manufactured by Million Zillion software, Inc.
[0119] 榭脂組成物（C)においては、室温クロ口ホルム不溶成分を1 H— NMRで分析するこ とによって、ブロック (b)の組成を計算することが出来る。 [0119] In the resin composition (C), the composition of the block (b) can be calculated by analyzing the room-temperature chloroform-insoluble component by 1 H-NMR.
[0120] 室温クロ口ホルム不溶成分中に含まれるブロック (b)に由来する成分の含有量が 0 . 1〜70重量％、好ましくは 0. 5〜50重量％、さらに好ましくは 1〜40重量％である 。室温クロ口ホルム不溶成分中に含まれるブロック (b)に由来する成分が検出される ことは、榭脂組成物（C)中において、ブロック (a)とブロック (b)とが互いに共有結合 で結合していることを示す。室温クロ口ホルム不溶成分中に含まれるブロック (b)に由 来する成分の含有量が上記範囲内にあるとォレフィン系ブロックポリマー (A2)の相 容化剤としての性能が向上し、島相の分散粒径が微細化し、機械的強度が向上する  [0120] The content of the component derived from the block (b) contained in the room temperature black mouth form insoluble component is 0.1 to 70% by weight, preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight. %. The fact that the component derived from block (b) contained in the room-temperature chloroform-insoluble component is detected is that block (a) and block (b) are covalently bonded to each other in rosin composition (C). Indicates that they are joined. When the content of the component derived from the block (b) contained in the room-temperature chloroform-insoluble component is within the above range, the performance of the olefin-based block polymer (A2) as a compatibilizer is improved, and the island phase is improved. The dispersed particle size of the material becomes finer and the mechanical strength is improved.
[0121] 室温クロ口ホルム不溶成分は以下のようにして測定する。 5gの榭脂組成物（C)を 1 00mlのキシレン還流中で溶解させる。 1Lのクロ口ホルムをホモジナイザーで攪拌し ている中に得られた溶液を注ぐ。ポリマーが析出し、スラリー状となった溶液を室温（1 5〜25°C)下で 10〜15時間静置した後、室温下で G3フィルターを用いてろ過し、濾 物と濾液とに分別する。濾物がクロ口ホルム不溶成分 (濾液力 Sクロ口ホルム可溶成分） となる。クロ口ホルム不溶成分中の組成分析を1 H— NMRで行ない、室温クロ口ホル ム不溶成分中に含まれるブロック (b)に由来する成分の含有量の重量％を測定する [0121] The room-temperature black-form insoluble component is measured as follows. 5 g of the rosin composition (C) is dissolved in 100 ml of xylene reflux. Pour the solution obtained while stirring 1 L of black mouth form with a homogenizer. The polymer precipitated and the slurry solution was allowed to stand at room temperature (15-25 ° C) for 10-15 hours, and then filtered using a G3 filter at room temperature. The product and the filtrate are separated. Filtrate becomes a black mouth form insoluble component (filtrate force S black mouth form soluble component). Perform composition analysis in the black insoluble component by 1 H-NMR, and measure the weight percentage of the component derived from the block (b) contained in the room temperature black insoluble component.
[0122] ォレフィン系ブロックポリマー (A2)は、触媒残查成分などの不純物含量が少なぐ 榭脂性状が良好であることが重合時に取り込まれた遷移金属含有量が lOOppm以 下であり、白色かつ遷移金属含有量が 50ppm以下であることがより好ましい。また、 ォレフィン系ブロックポリマー（A2)がパウダー状であるときはその平均粒径が 1〜1,0 OO /z m力つ JIS K6891に定められる方法で柳』定された嵩密度力 SO. 10〜0. 90g/ cm3の範囲にあることが好ましい。また、ォレフィン系ブロックポリマー（A2)はペレット 状、ノウダ一状、ベール状いずれの形態であっても使用することができる。 [0122] The olefin-based block polymer (A2) has a low content of impurities such as catalyst residue components and a good oleaginous property. The transition metal content incorporated during polymerization is less than lOOppm, More preferably, the transition metal content is 50 ppm or less. In addition, when the olefin-based block polymer (A2) is in the form of powder, the average particle size is 1 to 1,0 OO / zm, and the bulk density force determined by the method specified in JIS K6891 ”SO. 10 to It is preferably in the range of 90 g / cm 3 . Further, the olefin-based block polymer (A2) can be used in any form of pellets, noda-like, and veil.
[0123] <ォレフイン系ブロックポリマー（A2)の製造方法 >  [0123] <Method for producing olefin block polymer (A2)>
ォレフィン系ブロックポリマー（A2)は、例えば上記ハロゲン変性ポリオレフイン（a，） をマクロ開始剤として、ラジカル重合性単量体力も選ばれる 1種以上のモノマーを原 子移動ラジカル重合することにより製造することができる。なお、マクロ開始剤とは、原 子移動ラジカル重合の開始能を有する重合体であり、分子鎖中に原子移動ラジカル 重合の開始点となりうる部位を有する重合体を表す。  The olefin-based block polymer (A2) is produced, for example, by atom transfer radical polymerization of one or more monomers selected for radically polymerizable monomer power using the halogen-modified polyolefin (a,) as a macroinitiator. Can do. The macroinitiator is a polymer having the ability of initiating atom transfer radical polymerization, and represents a polymer having a site that can serve as an initiation point for atom transfer radical polymerization in the molecular chain.
[0124] 原子移動ラジカル重合とは、リビングラジカル重合の一つであり、有機ハロゲンィ匕物 又はハロゲン化スルホニル化合物を開始剤、遷移金属を中心金属とする金属錯体を 触媒としてラジカル重合性単量体をラジカル重合する方法である。具体的には、例え ば、 Matyjaszewskiら、 Chem. Rev., 101, 2921 (2001)、 WO96Z30421号パンフレット、 W097/18247号パンフレット、 WO98/01480号パンフレット、 WO98/40415号パン フレット、 WO00Z156795号パンフレット、あるいは澤本ら、 Chem. Rev., 101, 3689 (2 001)、特開平 8-41117号公報、特開平 9-208616号公報、特開 2000-264914号公報、 特開 2001-316410号公報、特開 2002-80523号公報、特開 2004-307872号公報など が挙げられる。用いられる開始剤としては、例えば有機ハロゲン化物やハロゲン化ス ルホニルイ匕合物が挙げられるが、特に炭素 炭素二重結合または炭素 酸素二重 結合の α位に存在する炭素 ハロゲン結合、あるいは一つの炭素原子上に複数の ノ、ロゲンが付加した構造が開始剤構造として好適である。ハロゲン変性ポリオレフィ ン (a')においては、炭素 炭素二重結合の α位に存在する炭素 ハロゲン結合、あ るいは一つの炭素原子上に複数のハロゲンが付加した構造を開始剤構造として利 用することができる。 [0124] Atom transfer radical polymerization is one of living radical polymerization, and is a radical polymerizable monomer using an organic halide or a sulfonyl halide as an initiator and a metal complex having a transition metal as a central metal as a catalyst. Is a method of radical polymerization. Specifically, for example, Matyjaszewski et al., Chem. Rev., 101, 2921 (2001), WO96Z30421 pamphlet, W097 / 18247 pamphlet, WO98 / 01480 pamphlet, WO98 / 40415 pamphlet, WO00Z156795 pamphlet, Alternatively, Sawamoto et al., Chem. Rev., 101, 3689 (2 001), JP-A-8-41117, JP-A-9-208616, JP-A 2000-264914, JP-A-2001-316410, JP 2002-80523 A, JP 2004-307872 A, and the like. Examples of the initiator used include organic halides and halogenated sulfonyl compounds. In particular, a carbon-halogen bond present at the α-position of a carbon-carbon double bond or a carbon-oxygen double bond, or a single carbon. Multiple on an atom In addition, a structure in which a rosin and a rogen are added is suitable as an initiator structure. In the halogen-modified polyolefin (a '), a carbon halogen bond existing at the α-position of the carbon-carbon double bond, or a structure in which multiple halogens are added on one carbon atom is used as an initiator structure. be able to.
[0125] ハロゲン変性ポリオレフイン (a')をマクロ開始剤として使用することによるォレフイン 系ブロックポリマー (A2)の製造方法は、基本的には上記変性ポリオレフイン (a')の 存在下、遷移金属を中心金属とする金属錯体を触媒としてラジカル重合性単量体を 原子移動ラジカル重合させるものである。  [0125] The production method of an olefin block polymer (A2) by using halogen-modified polyolefin (a ') as a macroinitiator is basically centered on transition metals in the presence of the modified polyolefin (a'). A radical polymerizable monomer is atom-transferred radically polymerized using a metal complex as a catalyst.
[0126] 重合触媒として用いられる遷移金属錯体としては特に限定されないが、好ましくは 周期表第 7族、 8族、 9族、 10族、または 11族元素を中心金属とする金属錯体である 。更に好ましいものとして、 0価の銅、 1価の銅、 2価のルテニウム、 2価の鉄又は 2価 のニッケルの錯体が挙げられる。なかでも、銅の錯体が好ましい。 1価の銅化合物を 具体的に例示するならば、塩化第一銅、臭化第一銅、ヨウ化第一銅、シアンィ匕第一 銅、酸化第一銅、過塩素酸第一銅等である。銅化合物を用いる場合、触媒活性を高 めるために 2,2 '—ビビリジル若しくはその誘導体、 1, 10—フエナント口リン若しくはそ の誘導体、又はテトラメチルエチレンジァミン、ペンタメチルジェチレントリァミン若しく はへキサメチルトリス（2—アミノエチル)ァミン等のポリアミン等が配位子として添加さ れる。また、 2価の塩化ルテニウムのトリストリフエ-ルホスフィン錯体 (RuCl (PPh ) )  [0126] The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element of the periodic table as a central metal. Further preferred are a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cyanide cuprous, cuprous oxide, cuprous perchlorate, etc. is there. In the case of using a copper compound, 2,2′-bibilidyl or a derivative thereof, 1,10-phenantorin or a derivative thereof, or tetramethylethylenediamine or pentamethyljetylenetriamine is used to increase the catalytic activity. Or a polyamine such as hexamethyltris (2-aminoethyl) amine is added as a ligand. Also, tristriphenylphosphine complex of divalent ruthenium chloride (RuCl (PPh))
2 3 3 も触媒として好適である。ルテニウム化合物を触媒として用いる場合は、活性化剤と してアルミニウムアルコキシド類が添加される。更に、 2価の鉄のビストリフエ-ルホス フィン錯体（FeCl (PPh ) )、 2価のニッケルのビストリフ ニルホスフィン錯体（NiCl (  2 3 3 is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, bivalent iron bistriphenylphosphine complex (FeCl (PPh)), divalent nickel bistriphenylphosphine complex (NiCl (
2 3 2 2 2 3 2 2
PPh ) )、及び、 2価のニッケルのビストリブチルホスフィン錯体（NiBr (PBu；) )も、触PPh)) and divalent nickel bistributylphosphine complex (NiBr (PBu;))
3 2 2 3 2 媒として好適である。 3 2 2 3 2 Suitable as a medium.
[0127] ラジカル重合性単量体力 選ばれる 1種以上のモノマーとしては、前述のブロック（ b)の項で例示したィ匕合物と同様のものが挙げられる。  Radical polymerizable monomer force [0127] Examples of the one or more monomers selected include the same compounds as those exemplified in the above-mentioned block (b).
[0128] ォレフィン系ブロックポリマー (A2)の製造方法において、重合方法は特に限定さ れず、塊状重合、溶液重合、懸濁重合、乳化重合、塊状 ·懸濁重合などを適用するこ とができる。ラジカル重合において使用できる溶媒としては、反応を阻害しないもので あれば何れでも使用することができる力 例えば、具体例として、ベンゼン、トルエン およびキシレン等の芳香族炭化水素系溶媒、ペンタン、へキサン、ヘプタン、ォクタ ン、ノナンおよびデカン等の脂肪族炭化水素系溶媒、シクロへキサン、メチルシクロ へキサンおよびデカヒドロナフタレンのような脂環式炭化水素系溶媒、クロ口ベンゼン 、ジクロロベンゼン、トリクロ口ベンゼン、塩化メチレン、クロ口ホルム、四塩化炭素およ びテトラクロルエチレン等の塩素化炭化水素系溶媒、メタノール、エタノール、 n—プ ロパノール、 iso—プロパノール、 n—ブタノール、 sec—ブタノールおよび tert—ブタノ ール等のアルコール系溶媒、アセトン、メチルェチルケトンおよびメチルイソブチルケ トン等のケトン系溶媒；酢酸ェチルおよびジメチルフタレート等のエステル系溶媒、ジ メチルエーテル、ジェチルエーテル、ジー n—ァミルエーテル、テトラヒドロフランおよ びジォキシァ-ソールのようなエーテル系溶媒等を挙げることができる。また、水を溶 媒として、懸濁重合、乳化重合することもできる。これらの溶媒は、単独でもまたは 2 種以上を混合して使用してもよい。また、これらの溶媒の使用によって、反応液が均 一相となることが好ましいが、不均一な複数の相となっても構わない。 [0128] In the production method of the olefin block polymer (A2), the polymerization method is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization, and the like can be applied. Solvents that can be used in radical polymerization are those that do not inhibit the reaction. Forces that can be used if any For example, as specific examples, aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane Solvents, cycloaliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, black benzene, dichlorobenzene, trichloro benzene, methylene chloride, black form, carbon tetrachloride and tetrachloro Chlorinated hydrocarbon solvents such as ethylene, methanol, ethanol, n- propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol alcohol solvents, acetone, methyl ethyl ketone and methyl Ketone solvents such as isobutyl ketone; Ester solvents such as methyl phthalate, di-methyl ether, Jefferies chill ether, di n - Amirueteru, tetrahydrofuran and Jiokishia - can be mentioned ether solvents such as sole or the like. In addition, suspension polymerization or emulsion polymerization can be performed using water as a solvent. These solvents may be used alone or in admixture of two or more. Moreover, it is preferable that the reaction liquid becomes a uniform phase by using these solvents, but a plurality of non-uniform phases may be used.
[0129] 反応温度はラジカル重合反応が進行する温度であれば何れでも構わず、所望する 重合体の重合度、使用するラジカル重合開始剤および溶媒の種類や量によって一 様ではないが、通常、— 100°C〜250°Cである。好ましくは— 50°C〜180°Cであり、 更に好ましくは 0°C〜160°Cである。反応は場合によって減圧、常圧または加圧の何 れでも実施できる。上記重合反応は、窒素やアルゴン等の不活性ガス雰囲気下で行 うことが好ましい。 [0129] The reaction temperature may be any temperature as long as the radical polymerization reaction proceeds, and is not uniform depending on the degree of polymerization of the desired polymer, the type and amount of the radical polymerization initiator and the solvent to be used. — 100 ° C ~ 250 ° C. Preferably, it is −50 ° C. to 180 ° C., more preferably 0 ° C. to 160 ° C. In some cases, the reaction can be carried out under reduced pressure, normal pressure or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
上記の方法により生成したォレフィン系ブロックポリマー (A2)は、重合に用いた溶媒 や未反応のモノマーの留去ある 、は非溶媒による再沈殿などの公知の方法を用いる ことにより単離される。更に、得られたポリマーをソックスレー抽出装置を用い、ァセト ンゃ THFなどの極性溶媒で処理することで、副生したホモラジカル重合体を除去す ることが可能である。  The olefin-based block polymer (A2) produced by the above method is isolated by using a known method such as distillation of the solvent used in the polymerization or unreacted monomer or reprecipitation with a non-solvent. Furthermore, by treating the obtained polymer with a polar solvent such as acetonitrile or THF using a Soxhlet extraction apparatus, it is possible to remove the by-product homoradical polymer.
[0130] 《パウダー状のォレフィン系ブロックポリマー（A2)の製造方法》 [0130] <Production method of powdery olefin-based block polymer (A2)>
ォレフィン系ブロックポリマー (A2)の製造方法としては、上述した製造方法により製 造したォレフィン系ブロックポリマー (A2)を適当な溶媒中に均一溶解させた後に晶 析する方法や、ォレフィン系ブロックポリマー (A2)を機械粉砕する方法、平均粒径が 1〜1,000 ！!1かっ嵩密度が0. 10〜0. 50gZcm3であるパウダー状のハロゲン変 性ポリオレフイン (Α' )をマクロ開始剤として、ラジカル重合性単量体力も選ばれる 1 種以上のモノマーを、パウダー状のハロゲン変性ポリオレフイン (Α' )が非溶融状態 で原子移動ラジカル重合することにより製造する方法などが挙げられる。またパウダ 一状のハロゲン変性ポリオレフイン (Α，）の平均粒径は 1〜500 mであることがより 好ましい。 The olefin-based block polymer (A2) can be produced by uniformly dissolving the olefin-based block polymer (A2) produced by the above-described production method in an appropriate solvent. For analysis, olefinic block polymer (A2) by mechanical pulverization, average particle size of 1 to 1,000! ! 1 Powdery halogen-modified polyolefin (Α ') with a bulk density of 0.10 to 0.50 gZcm 3 For example, a method in which the halogen-modified polyolefin (Α ′) is produced by atom transfer radical polymerization in a non-molten state. The average particle size of the powdery halogen-modified polyolefin (Α) is more preferably 1 to 500 m.
ォレフィン系ブロックポリマー (A2)を工業的に用いる場合、触媒成分などの不純物 含有量の少ない良性状で得られることが好ましい。具体的には、平均粒径が 1〜 1,0 OO /z mかつ嵩密度が 0. 10-0. 90gZcm3のパウダー状であることが好ましい。ノ ウダ一性状を制御する過程は、ォレフィン系ブロックポリマー (A2)を製造するあらゆ る工程において実施することが可能である力 原料のポリオレフインを製造する工程、 つまりォレフィン類を重合する工程において触媒や重合条件を制御することによる方 法や、晶析による方法などにより制御する方法が好ましく用いられる。晶析による方 法としては、原料のポリマーすなわち通常粒子状あるいはペレット状のポリマーをあら 力じめ晶析操作により良性状のパウダーに変換し、このモルホロジーを保持しつつォ レフイン系ブロックポリマー (A2)を製造する方法、マクロ開始剤を調製する工程にお Vヽて晶析操作を行い良性状のパウダーに変換し、このモルホロジーを保持しつつォ レフイン系ブロックポリマー（A2)を製造する方法、もしくはォレフィン系ブロックポリマ 一 (A2)を製造した後に晶析操作により良性状のパウダーに変換する方法などが好 ましく用いられる。晶析操作では、ポリマーを良溶媒に溶解させた後、貧溶媒を加え たり、降温させたりすることにより、ポリマー粒子を析出させることで、粒径や嵩密度を コントロールすることが可能となる。晶析操作により、粒径や嵩密度をコントロールす る因子として、ポリマー濃度、良溶媒種、貧溶媒種、攪拌速度、降温速度、などが重 要となる。晶析操作における良溶媒としては、ポリマーを溶解または膨潤させ得る物 であれば、特に限定されるものではぐ溶解させようとするポリマーの種類に応じて一 種類以上の溶媒を選ぶことが可能であるが、通常ポリオレフイン類に親和性が高 、 溶媒として、芳香族炭化水素系溶媒もしくは脂肪族炭化水素系溶媒が好ましく用い られ、中でも、トルエン、キシレン、クロ口ベンゼン、デカンあるはいそれらの混合溶媒 等が特に好ましく用いられる。また、ポリエチレンやポリプロピレンなど、室温以上に 融点を有するポリオレフインを含む場合、室温では溶解しにくいため前記溶媒中でカロ 熱することで溶解させることが可能となる。このときのポリマー濃度として、通常 5gZL 〜500gZL、好ましくは、 10gZL〜300gZLの範囲である。 When the olefin-based block polymer (A2) is used industrially, it is preferably obtained in a benign state with a low content of impurities such as catalyst components. Specifically, the powder is preferably in the form of a powder having an average particle size of 1 to 1,0 OO / zm and a bulk density of 0.10-0.90 gZcm 3 . The process for controlling the properties of the noda can be carried out in any process for producing the olefin-based block polymer (A2). The process for producing the raw polyolefin, that is, the process for polymerizing olefins. And a method of controlling by polymerization method or a method of controlling by crystallization method is preferably used. As a method of crystallization, a raw material polymer, that is, a normal particle-like or pellet-like polymer is preliminarily converted into a benign powder by a crystallization operation, and the olefin-based block polymer (A2) is retained while maintaining this morphology. ), A method for producing an olefin block polymer (A2) while maintaining this morphology, by performing a crystallization operation in the step of preparing a macroinitiator and converting it into a benign powder. Alternatively, a method in which an olefin-based block polymer (A2) is produced and then converted into a benign powder by a crystallization operation is preferably used. In the crystallization operation, it is possible to control the particle diameter and bulk density by precipitating polymer particles by dissolving the polymer in a good solvent and then adding a poor solvent or lowering the temperature. The factors such as polymer concentration, good solvent species, poor solvent species, stirring speed, temperature drop rate, etc. are important factors for controlling the particle size and bulk density by crystallization operation. The good solvent in the crystallization operation is not particularly limited as long as it can dissolve or swell the polymer, and one or more solvents can be selected depending on the type of polymer to be dissolved. However, usually it has a high affinity for polyolefins, and an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent is preferably used as the solvent. Of these, toluene, xylene, black benzene, decane or a mixed solvent thereof are particularly preferably used. In addition, when a polyolefin having a melting point above room temperature, such as polyethylene or polypropylene, is difficult to dissolve at room temperature, it can be dissolved by heating in the solvent. The polymer concentration at this time is usually in the range of 5 gZL to 500 gZL, preferably 10 gZL to 300 gZL.
[0132] 晶析操作における貧溶媒としては、ポリマーを析出させ得る溶媒であれば、特に限 定されるものではぐ溶解させようとするポリマーの種類に応じて一種類以上の溶媒を 選ぶことが可能である。晶析操作を行う場合、通常攪拌速度を上昇させることで粒径 を小さくすることが可能である。また、降温させることにより、ポリマーを析出させる場 合、一般的に、ポリマーが析出する温度の前後で降温速度をゆっくりすることが好ま しい。このときの降温速度として、通常 5°CZhr〜100°CZhr、好ましくは 5°CZhr〜 50°CZhrである。 [0132] The poor solvent in the crystallization operation is not particularly limited as long as it is a solvent capable of precipitating the polymer, and one or more solvents may be selected depending on the type of polymer to be dissolved. Is possible. When performing the crystallization operation, it is usually possible to reduce the particle size by increasing the stirring speed. Further, when the polymer is precipitated by lowering the temperature, it is generally preferable to slow the temperature lowering rate before and after the temperature at which the polymer is precipitated. The temperature lowering rate at this time is usually 5 ° CZhr to 100 ° CZhr, preferably 5 ° CZhr to 50 ° CZhr.
[0133] このような性状の良好なォレフィン系ブロックポリマー (A2)を製造する手法は、ポリ ォレフィン部分の融点が 80°C以上、好ましくは 100°C以上の場合に特に好ましく用 いられる。  [0133] Such a method for producing an olefin-based block polymer (A2) having good properties is particularly preferably used when the melting point of the polyolefin portion is 80 ° C or higher, preferably 100 ° C or higher.
[0134] また、粒子性状を良好に制御したポリマーは、遠心分離やろ過操作により、溶媒の みならず、製造段階で発生した有機物残渣、触媒残查、などの不純物を容易に除去 することが可能であり、粒子性状が不均質なポリマーに比べ工業的に有利である。  [0134] In addition, a polymer having a well-controlled particle property can easily remove not only the solvent but also impurities such as organic residues and catalyst residues generated in the production stage by centrifugation and filtration operations. It is possible and is industrially advantageous compared to polymers with heterogeneous particle properties.
[0135] ォレフィン系ブロックポリマー (A2)の製造方法は、原子移動ラジカル重合開始時、 あるいは、重合中にパウダー状のハロゲン変性ポリオレフイン (Α' )であるマクロ開始 剤が非溶融状態で原子移動ラジカル重合が進行することを特徴とする。  [0135] The production method of the olefin-based block polymer (A2) is carried out at the start of atom transfer radical polymerization, or during the polymerization, the macroinitiator that is a powdery halogen-modified polyolefin (Α ') is in an unmolten state with an atom transfer radical. Polymerization proceeds.
[0136] 原子移動ラジカル重合においては、溶媒を使用してもしなくても良い。使用できる 溶媒としては、反応を阻害しないものであれば何れでも使用することができるが、例え ば、具体例として、ベンゼン、トルエンおよびキシレン等の芳香族炭化水素系溶媒、 ペンタン、へキサン、ヘプタン、オクタン、ノナンおよびデカン等の脂肪族炭化水素系 溶媒、シクロへキサン、メチルシクロへキサンおよびデカヒドロナフタレンのような脂環 式炭化水素系溶媒、クロ口ベンゼン、ジクロロベンゼン、トリクロ口ベンゼン、塩化メチ レン、クロ口ホルム、四塩ィ匕炭素およびテトラクロルエチレン等の塩素化炭化水素系 溶媒、メタノール、エタノール、 n—プロパノール、 。 プロパノール、 n—ブタノール 、 sec ブタノールおよび tert ブタノール等のアルコール系溶媒、アセトン、メチルェ チルケトンおよびメチルイソブチルケトン等のケトン系溶媒；酢酸ェチルおよびジメチ ルフタレート等のエステル系溶媒、ジメチルエーテル、ジェチルエーテル、ジ—n— ァミルエーテル、テトラヒドロフランおよびジォキシァ-ソールのようなエーテル系溶媒 等を挙げることができる。また、水を溶媒とすることもできる。これらの溶媒は、単独で もまたは 2種以上を混合して使用してもょ 、。 [0136] In atom transfer radical polymerization, a solvent may or may not be used. Any solvent can be used as long as it does not inhibit the reaction. For example, specific examples include aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane and heptane. Aliphatic hydrocarbon solvents such as cyclohexane, octane, nonane, and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and decahydronaphthalene, chlorobenzene, dichlorobenzene, trichlorobenzene, methyl chloride Chlorinated hydrocarbons such as len, black mouth form, tetrasalt carbon and tetrachloroethylene Solvent, methanol, ethanol, n -propanol,. Alcohol solvents such as propanol, n -butanol, sec butanol and tert butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, jetyl ether, di- Examples thereof include ether solvents such as n -amyl ether, tetrahydrofuran and dioxy-sol. Water can also be used as a solvent. These solvents can be used alone or in admixture of two or more.
[0137] 反応温度はマクロ開始剤であるパウダー状のハロゲン変性ポリオレフイン (Α' )が溶 融または膨潤しない温度でかつラジカル重合反応が進行する温度であれば何れで も構わず、所望する重合体の重合度、使用するラジカル重合開始剤および溶媒の種 類や量によって一様ではないが、通常、 100°C〜250°Cである。好ましくは— 50 °C〜120°Cであり、更に好ましくは 0°C〜100°Cである。反応は場合によって減圧、 常圧または加圧の何れでも実施できる。上記重合反応は、窒素やアルゴン等の不活 性ガス雰囲気下で行うことが好ま 、。  [0137] The reaction temperature may be any temperature as long as the powdery halogen-modified polyolefin (Α '), which is a macroinitiator, does not melt or swell, and the radical polymerization reaction proceeds. Although it is not uniform depending on the degree of polymerization, the type of radical polymerization initiator used, and the solvent, it is usually 100 ° C to 250 ° C. Preferably, it is −50 ° C. to 120 ° C., more preferably 0 ° C. to 100 ° C. In some cases, the reaction can be carried out under reduced pressure, normal pressure, or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
[0138] 具体的には、例えば以下のようにして、パウダー状のォレフィン系ブロックポリマー（ A2)を製造することができる。  [0138] Specifically, for example, the powdery olefin-based block polymer (A2) can be produced as follows.
[0139] 窒素置換したガラス製反応器に、ハロゲン原子を含有したパウダー状のハロゲン変 性ポリオレフイン (A，）と、トルエン等の有機溶媒と、メタクリル酸メチル等のラジカル重 合性のモノマーとを入れ、 80°Cに加熱攪拌してポリマーをスラリー状に分散させる。 このスラリー溶液に、臭化銅および N,N,N',N",N"—ペンタメチルジェチレントリアミ ン（PMDETA)をカ卩え、 80°Cで 1. 5時間重合を行う。反応液にメタノールをカ卩えてポ リマーを濾別'洗浄し、析出したポリマーを減圧乾燥することによって、パウダー状の ォレフィン系ブロックポリマー（A2)が得られる。  [0139] A nitrogen-substituted glass reactor is charged with a powdery halogen-modified polyolefin (A,) containing a halogen atom, an organic solvent such as toluene, and a radical-polymerizable monomer such as methyl methacrylate. And heat and stir to 80 ° C to disperse the polymer in a slurry. Into this slurry solution is added copper bromide and N, N, N ', N ", N" -pentamethyljetylene triamine (PMDETA), and polymerization is carried out at 80 ° C for 1.5 hours. Methanol is added to the reaction solution, the polymer is filtered and washed, and the precipitated polymer is dried under reduced pressure to obtain a powdery olefin-based block polymer (A2).
[0140] 上記の方法により生成したパウダー状のォレフィン系ブロックポリマー (A2)は、重 合に用いた触媒残渣ゃ溶媒や未反応のモノマーを簡単な濾過 ·洗浄、ある！ヽは遠心 分離操作などにより除去することができる。  [0140] The powdery olefin-based block polymer (A2) produced by the above method has a simple filtration / washing of the catalyst residue, solvent and unreacted monomer used for polymerization! The soot can be removed by centrifugation.
[0141] 〔樹脂 (B)〕  [0141] [Resin (B)]
次に、本発明で用いられる榭脂 (B)について説明する。 <ポリカーボネート榭脂 (bl) > Next, the resin (B) used in the present invention will be described. <Polycarbonate resin (bl)>
本発明で用いられるポリカーボネート榭脂（bl)は、ビスフエノール Aなどの 2価フエ ノールと、炭酸ジエステルあるいはホスゲンと力も得られる従来公知のポリカーボネー トである。  The polycarbonate resin (bl) used in the present invention is a conventionally known polycarbonate capable of obtaining power with a divalent phenol such as bisphenol A and a carbonic acid diester or phosgene.
[0142] 2価フエノールとしては、 2,2—ビス（4—ヒドロキシフエ-ル）プロパン [ビスフエノー ル A]の他に、 1,1—ビス（4—ヒドロキシフエ-ル)メタン、 1,1—ビス（4—ヒドロキシフ ェ -ル）ェタン、 2,2—ビス（4ーヒドロキシフエ-ル）ブタンなどのビス（ヒドロキシァリー ル）アルカン類、 1, 1—ビス（4 -ヒドロキシフエ-ル）シクロへキサンなどのビス (ヒドロキ シァリール)シクロアルカン類、 4,4'ージヒドロキシジフエ-ルエーテルなどのジヒドロ キシァリールエーテル類、ジヒドロキシジァリールスルフイド類などが例示される。  [0142] Divalent phenol includes 2,2-bis (4-hydroxyphenol) propane [bisphenol A], 1,1-bis (4-hydroxyphenol) methane, 1,1 —Bis (hydroxyl) alkanes such as bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenol) butane, 1,1-bis (4-hydroxyphenol) Examples thereof include bis (hydroxyl) cycloalkanes such as cyclohexane, dihydroxyl ethers such as 4,4′-dihydroxydiphenyl ether, and dihydroxydiarylsulfides.
[0143] これらの 2価フエノールは、必要に応じて 2種類以上を用いてもよぐ通常は、ビスフ エノール八、またはビスフエノール Aを主成分とし、少量の他の 2価フエノールが含ん だものが使用される。  [0143] Two or more kinds of these divalent phenols may be used if necessary. Usually, bisphenol 8 or bisphenol A is the main component, and a small amount of other divalent phenols is contained. Is used.
[0144] 炭酸ジエステルとしては、ジフエ-ルカーボネート、ジトリールカーボネート、ビス（ク ロロフエニル）カーボネート、ビス（ジフエニル）カーボネート、ジェチノレカーボネートな どが挙げられる。このうち、ジフエ-ルカーボネートが好適に使用される。  [0144] Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, bis (diphenyl) carbonate, and jetinore carbonate. Of these, diphenyl carbonate is preferably used.
[0145] また、ポリカーボネートは、必要に応じて、ァリロキシ化合物、モノカルボキシィ匕合物 などの末端封止剤で処理されたものであってもょ 、。 [0145] The polycarbonate may be treated with an end-capping agent such as an aryloxy compound or a monocarboxy compound if necessary.
くアクリル系榭脂 (b2) >  Acrylic resin (b2)>
本発明で用いられるアクリル系榭脂 (b2)は、アクリル酸エステルの重合体 (ポリアク リレート）、メタクリル酸エステルの重合体 (ポリメタタリレート）、およびそれらの共重合 体榭脂などが挙げられる。  Examples of the acrylic resin (b2) used in the present invention include an acrylic ester polymer (polyacrylate), a methacrylic ester polymer (polymetatalylate), and a copolymer resin thereof.
[0146] ポリアタリレートとして具体的には、ポリメチルアタリレート、ポリェチルアタリレート、 ポリブチルアタリレート、ポリ 2—ェチルへキシルアタリレート、ポリイソブチルアタリレー ト、ポリ n キシルアタリレート、ポリ n—ォクチルアタリレート、ポリラウリルアタリレート[0146] Specifically, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly 2-ethyl hexyl acrylate, polyisobutyl acrylate, poly n xyl acrylate, poly n—Octyl acrylate, polylauryl acrylate
、ポリステアリルアタリレートなどが挙げられる。 And polystearyl acrylate.
[0147] ポリメタタリレートとして具体的には、ポリメチルメタタリレート、ポリェチルメタクリレー ト、ポリブチノレメタタリレート、ポリラウリノレメタタリレート、ポリステアリノレメタタリレート、ポ リイソブチノレメタタリレート、ポリ n—へキシノレメタタリレート、ポリ n—ォクチノレメタクリレ ートなどが挙げられる。上記のようなアクリル系榭脂 (b2)は、 1種単独で、あるいは 2 種以上組み合わせて用いることができる。 [0147] Specific examples of the polymetatalate include polymethyl metatalylate, polyethyl methacrylate, polybutinoremethalate, polylaurinoremethalate, polystearinolemetalate, Examples thereof include lysobutynole methacrylate, poly n-hexino methacrylate, poly n-octino methacrylate. The acrylic resin (b2) as described above can be used alone or in combination of two or more.
[0148] アクリル系榭脂（b2)の分子量は、数平均分子量で 500〜 10,000の範囲にあること が好ましぐさらには 1,000〜5,000の範囲にあることがより好ましい。なおここでいう 数平均分子量とは、 GPCを用いポリスチレンを標準として得られたものである。 [0148] The molecular weight of the acrylic resin (b2) is preferably in the range of 500 to 10,000 as the number average molecular weight, and more preferably in the range of 1,000 to 5,000. Here, the number average molecular weight is obtained using GPC and polystyrene as a standard.
[0149] このようなアクリル系榭脂 (b2)は、溶液重合法、懸濁重合法、塊状重合法等、公知 の重合法で製造することができる。 [0149] Such an acrylic resin (b2) can be produced by a known polymerization method such as a solution polymerization method, a suspension polymerization method, or a bulk polymerization method.
<ビニル重合体（b3) >  <Vinyl polymer (b3)>
本発明で用いられるビュル重合体 (b3)は、芳香族ビニル化合物 (ml)およびシァ ン化ビニル化合物（m2)力 選ばれる 1種以上を含んでなるビュルモノマーから得ら れる重合体である。  The bull polymer (b3) used in the present invention is a polymer obtained from a bull monomer comprising at least one selected from an aromatic vinyl compound (ml) and a vinyl cyanide compound (m2).
[0150] 芳香族ビュル化合物（ml)としては、スチレン、ビュルトルエン、 a—メチルスチレン 、クロルスチレン、スチレンスルホン酸及びその塩等が挙げられる。 [0150] Examples of the aromatic bur compound (ml) include styrene, butyltoluene, a -methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof.
[0151] シアン化ビュル化合物（m2)としては、アクリロニトリル、メタタリ口-トリル等が挙げら れる。  [0151] Examples of the cyanide bur compound (m2) include acrylonitrile and meta-tallow-tolyl.
[0152] 本発明で用いられるビュル重合体 (b3)は、原料モノマーとして上記以外の他のビ 二ルイ匕合物、例えばジェン等を用いることができる。  [0152] In the bulle polymer (b3) used in the present invention, other vinyl compounds other than those described above, such as Gen, can be used as a raw material monomer.
[0153] ジェンとしては、ブタジエン、イソプレン、 4ーメチルー 1,3 ペンタジェン、 1,3 ぺ ンタジェン、 1,4 ペンタジェン、 1,5 へキサジェン、 1,4一へキサジェン、 1,3 へ キサジェン、 1,3—才クタジェン、 1,4ーォクタジェン、 1,5—才クタジェン、 1,6 オタ タジェン、 1,7—ォクタジェン等が挙げられる。  [0153] The gens include butadiene, isoprene, 4-methyl-1,3 pentagen, 1,3 pentagen, 1,4 pentagen, 1,5 hexagen, 1,4 one hexagen, 1,3 hexagen, 1, Examples include 3-aged Tatageng, 1,4-Octagen, 1,5-Old Tajtagen, 1,6 Otaj Tagen, and 1,7-Octagen.
[0154] ビニル重合体 (b3)としては、芳香族ビニル化合物 (ml)の単独重合体 (例えばポリ スチレン等）、芳香族ビニル化合物 (ml)とジェンとの共重合体 (例えばブタジエン' スチレン共重合体等）、芳香族ビニル化合物 (ml)とシアン化ビニル化合物 (m2)と の共重合体 (例えばアクリロニトリル 'スチレン共重合体等）、芳香族ビニル化合物 (m 1)とシアン化ビニル化合物 (m2)とジェンとの共重合体 (例えばアクリロニトリル ·ブタ ジェン ·スチレン共重合体等）が挙げられる。 [0155] 本発明で用いられビュル重合体 (b3)は、従来公知の方法により製造することがで き、また、ビニル重合体 (b3)は、市販品を使用することもできる。 [0154] Examples of the vinyl polymer (b3) include a homopolymer of an aromatic vinyl compound (ml) (eg, polystyrene), and a copolymer of an aromatic vinyl compound (ml) and gen (eg, butadiene / styrene copolymer). Polymer), a copolymer of aromatic vinyl compound (ml) and vinyl cyanide compound (m2) (for example, acrylonitrile 'styrene copolymer, etc.), aromatic vinyl compound (m 1) and vinyl cyanide compound ( and a copolymer of m2) and gen (for example, acrylonitrile / butadiene / styrene copolymer). [0155] The bull polymer (b3) used in the present invention can be produced by a conventionally known method, and a commercially available product can be used as the vinyl polymer (b3).
<ポリフエ-レンオキサイド（b4) >  <Polyphenylene oxide (b4)>
本発明で用いられるポリフエ-レンオキサイド (b4)としては、例えばポリ（2,6 ジメ チル 1 ,4 フエ二レン）エーテル、ポリ（2 メチル 6 ェチル 1 ,4 フエ二レン） エーテル、ポリ（2,6 ジェチルー 1,4 フエ-レン）エーテル、ポリ（2 ェチルー 6— n プロピノレ - 1,4-フエ-レン）エーテノレ、ポリ（2,6 ジ n-プロピル - 1,4-フエ二 レン）エーテル、ポリ（2—メチルー 6—n-ブチルー 1,4 フエ-レン）エーテル、ポリ（ 2 -ェチル 6 イソプロピル - 1,4-フエ-レン）エーテル、ポリ（2—メチル 6 ク ロロ一 1,4 フエ二レン）エーテル、ポリ（2—メチル 6 ヒドロキシェチル一 1,4 フ ェニレン）エーテル、ポリ（2 メチル 6 クロロェチノレ - 1,4-フエ二レン）エーテノレ などが挙げられる。また、これらのポリフエ-レンオキサイドをポリスチレン、ポリアミドな どで変性させて得られる変性ポリフエ-レンオキサイドが挙げられる。  Examples of the polyphenylene oxide (b4) used in the present invention include poly (2,6 dimethyl 1,4 phenylene) ether, poly (2 methyl 6 ethyl 1,4 phenylene) ether, poly (2 , 6 Jetyl 1,4 Phenylene) ether, Poly (2 Ethyl 6—n Propinole-1,4-Phenylene) etherole, Poly (2,6 Di n-propyl-1,4-Phenylene) ether , Poly (2-methyl-6-n-butyl-1,4 phenylene) ether, poly (2-ethyl-6 isopropyl-1,4-phenylene) ether, poly (2-methyl-6 chloro 1,4 For example, phenyl) ether, poly (2-methyl-6-hydroxyethyl-1,4phenylene) ether, poly (2-methyl-6-chloroethylenol-1,4-phenylene) etherole. Moreover, modified polyphenylene oxide obtained by modifying these polyphenylene oxides with polystyrene, polyamide or the like can be mentioned.
〔樹脂組成物 (C)〕  [Resin composition (C)]
<添加剤 >  <Additives>
本発明の榭脂組成物 (C)中には、その目的、効果を大きく阻害しない範囲で、用 途に応じて各種の公知の添加剤を配合すること準できる。用いることのできる添加剤 としては、たとえば、分散剤、滑剤、可塑剤、難燃剤、酸化防止剤、帯電防止剤、光 安定剤、紫外線吸収剤、結晶化促進剤 (増核剤)等の改質用添加剤、顔料、染料等 の着色剤、カーボンブラック、酸ィ匕チタン等が挙げられる。また、タルク、クレー、マイ 力、けい酸塩類、炭酸塩類等の粒子状充填物、ガラス繊維、ワラストナイト等の繊維 状充填剤、チタン酸カリウム等のウイスカーを配合することもできる。  Various known additives can be blended in the resin composition (C) of the present invention in accordance with the application within a range that does not significantly impair its purpose and effect. Examples of additives that can be used include modified dispersants, lubricants, plasticizers, flame retardants, antioxidants, antistatic agents, light stabilizers, ultraviolet absorbers, and crystallization accelerators (nucleating agents). Quality additives, colorants such as pigments and dyes, carbon black, titanium oxide, and the like. Moreover, particulate fillers such as talc, clay, strength, silicates and carbonates, fibrous fillers such as glass fiber and wollastonite, and whiskers such as potassium titanate can also be blended.
[0156] <榭脂組成物（C)の組成 > [0156] <Composition of rosin composition (C)>
本発明の榭脂組成物（C)を構成するポリオレフイン (A1)、ォレフィン系ブロックポリ マー (A2)、および、榭脂（B)の組成比は、 3者の和を 100重量％とした場合におい て、成分 (A1)は、通常 1〜98. 9重量％、好ましくは 5〜90重量％である。成分 (A1 )が 1重量％よりも少ないと耐溶剤性が低下し、 98. 9重量％よりも多いと衝撃強度や 曲げ強度が低下する。また、成分 (A2)は、通常 0. 1〜50重量％、好ましくは 0. 5〜 30重量％である。成分 (A2)が 0. 1重量％より少ないと相容化剤としての効果が低 下し、 50重量％よりも多いと機械物性が低下する。また、成分 (B)は、通常 1〜98. 9 重量％、好ましくは 9. 5〜95. 5重量％である。成分 (B)が 1質量％より少ないと機械 物性が低下し、 98. 9重量％よりも多いと耐溶剤性が低下する。また、榭脂組成物の 物性を低下させない範囲で、ポリオレフイン (A1)、ポリオレフイン系ブロックポリマー（ A2)、および榭脂 (B)以外の榭脂が含まれて!/ヽても良!、。 The composition ratio of the polyolefin (A1), the olefin-based block polymer (A2), and the resin (B) constituting the resin composition (C) of the present invention is 100% by weight when the sum of the three is 100% by weight. In this connection, the component (A1) is usually 1 to 98.9% by weight, preferably 5 to 90% by weight. When the component (A1) is less than 1% by weight, the solvent resistance is lowered, and when it is more than 98.9% by weight, the impact strength and the bending strength are lowered. The component (A2) is usually 0.1 to 50% by weight, preferably 0.5 to 30% by weight. If the component (A2) is less than 0.1% by weight, the effect as a compatibilizer will be reduced, and if it is more than 50% by weight, the mechanical properties will be reduced. The component (B) is usually 1 to 98.9% by weight, preferably 9.5 to 95.5% by weight. If the component (B) is less than 1% by mass, the mechanical properties are degraded, and if it is greater than 98.9% by weight, the solvent resistance is degraded. In addition, other than the polyolefin (A1), the polyolefin block polymer (A2), and the resin (B), the resin may be included as long as the physical properties of the resin composition are not deteriorated.
[0157] 本発明に係る榭脂組成物（C)は、室温クロ口ホルム不溶成分中の溶解度パラメ一 タが 18〜25j/mの範囲にあるビュルモノマーの重合体の含有量が 0. 1〜50重量 %、好ましくは 0. 3〜30重量％、さらに好ましくは 0. 5〜20重量％の範囲にある。  [0157] The resin composition (C) according to the present invention has a content of a polymer of a bull monomer having a solubility parameter in a room-temperature chloroform-insoluble component in the range of 18 to 25 j / m. -50% by weight, preferably 0.3-30% by weight, more preferably 0.5-20% by weight.
[0158] また、本発明に係る榭脂組成物 (C)は、榭脂 (B)がポリフ -レンオキサイド (b4) である場合には、室温クロ口ホルム不溶成分中の溶解度パラメータが 18〜25j/m の範囲にあるビュルモノマーの重合体の重量（C )と、室温クロ口ホルム可溶成分  [0158] In addition, in the composition of the resin (C) according to the present invention, when the resin (B) is polyphenylene oxide (b4), the solubility parameter in the room-temperature chloroform-insoluble component is 18 to The weight (C) of the polymer of butyl monomer in the range of 25j / m and room temperature black mouth form soluble component
insol  insol
中の溶解度パラメータが 18〜25jZmの範囲にあるビュルモノマーの重合体の重量 (C )との比（C /C )カ 〜 100、好ましくは 10〜： L00、より好ましくは 30〜： L00 sol insol sol  The ratio (C / C) to the weight (C) of the polymer of the butyl monomer having a solubility parameter in the range of 18 to 25 jZm (C / C) -100, preferably 10-: L00, more preferably 30-: L00 sol insol sol
である。  It is.
[0159] 榭脂組成物（C)の室温クロ口ホルム不溶成分中の溶解度パラメータが 18〜25JZ mの範囲にあるビュルモノマーの重合体は、上述したようにォレフィン系ブロックポリ マー (A2)に由来するもの（ブロック (a)に共有結合で結合したブロック (b) )であり、 榭脂組成物の室温クロ口ホルム可溶成分中の溶解度パラメータが 18〜25j/mの範 囲にあるビュルモノマーの重合体は、組成物中に単独で存在する（ポリオレフイン成 分と結合していない）ビュルモノマーの重合体である。したがって（C /C )の値に  [0159] As described above, a polymer of bulle monomer having a solubility parameter in the room-temperature chloroform-insoluble component of the rosin composition (C) in the range of 18 to 25 JZm can be converted into an olefin-based block polymer (A2). A bulule with a solubility parameter in the soluble component of room temperature black mouth form of the coconut resin composition in the range of 18-25j / m. The monomer polymer is a polymer of bulle monomers that are present alone (not bound to the polyolefin component) in the composition. Therefore, the value of (C / C)
insol sol より組成物中のビュルモノマーの重合体がォレフィン系ブロックポリマー（A2)に由来 するものであるどうかが分かる。  It can be seen from insol sol whether the polymer of the bull monomer in the composition is derived from the olefin block polymer (A2).
[0160] なお、組成物の室温クロ口ホルム不溶成分中の溶解度パラメータが 18〜25jZm の範囲にあるビュルモノマーの重合体の重量（C )と、組成物の室温クロ口ホルム [0160] It should be noted that the weight (C) of the polymer of the bull monomer whose solubility parameter in the room temperature black mouth form insoluble component of the composition is in the range of 18 to 25 jZm, and the room temperature black mouth form of the composition
insol  insol
可溶成分中の溶解度パラメータが 18〜25jZmの範囲にあるビニルモノマーの重合 体の重量（C )は以下のようにして求める。  The weight (C) of the vinyl monomer polymer having a solubility parameter in the soluble component in the range of 18 to 25 jZm is determined as follows.
sol  sol
[0161] 5gの榭脂組成物（C)を 100mlのキシレン還流中で溶解させる。 1Lのクロ口ホルム をホモジナイザーで攪拌している中に得られた溶液を注ぐ。ポリマーが析出し、スラリ 一状となった溶液をろ過し、濾物と濾液とに分別する。濾物がクロ口ホルム不溶成分 ( 濾液がクロ口ホルム可溶成分）となる。クロ口ホルム不溶成分中の組成分析を1 H— N MRで行ない、室温クロ口ホルム不溶成分中に含まれるブロック (b)に由来する成分 の含有量の重量％を測定する。クロ口ホルム可溶成分中の組成分析を1 H— NMRで 行ない、ブロック (b)と同質の成分について榭脂組成物（C)中の重量％を測定する。 [0161] 5 g of the resin composition (C) is dissolved in 100 ml of xylene reflux. 1L black mouth holm Pour the solution obtained while stirring with a homogenizer. The solution in which the polymer is precipitated and becomes a slurry is filtered and separated into a filtrate and a filtrate. The filtrate becomes a black mouth form insoluble component (the filtrate becomes a black mouth form soluble component). The composition analysis in the black mouth form insoluble component is performed with 1 H—N MR, and the weight% of the content derived from the block (b) contained in the room temperature black mouth form insoluble component is measured. The composition analysis of the black mouth form soluble component is carried out by 1 H-NMR, and the weight percent in the rosin composition (C) is measured for the same component as the block (b).
[0162] く榭脂組成物 (C)の調製法 > [0162] Preparation Method of Coffin Composition (C)>
本発明の榭脂組成物 (C)の調製方法としては、特に限定されるものではなぐ溶融 法、溶液法等の公知の方法によって調整することが可能であり、実用的には溶融混 練方法が好ましい。  The preparation method of the resin composition (C) of the present invention is not particularly limited and can be adjusted by a known method such as a melting method or a solution method, and practically a melt-kneading method. Is preferred.
[0163] 溶融混練の方法としては、熱可塑性榭脂について一般に実用されている混練方法 をそのまま適用することができる。たとえば、粉状又は粒状の各成分、及び、必要で あれば付カ卩的成分を、ヘンシェルミキサー、リボンブレンダー、 V型ブレンダ一等によ り均一にドライ混合した後、一軸又は多軸混練押出機、混練ロール、バッチ混練機、 ニーダー、バンノリーミキサー等で溶融混練することができる。  [0163] As a method of melt-kneading, a kneading method generally used for thermoplastic resin can be applied as it is. For example, powdery or granular components, and optional components if necessary, are uniformly dry mixed with a Henschel mixer, ribbon blender, V-type blender, etc., and then uniaxial or multiaxial kneading extrusion Melting and kneading can be performed with a machine, a kneading roll, a batch kneader, a kneader, a vannolly mixer or the like.
[0164] 各成分の溶融混練温度 (たとえば、押出機ならシリンダー温度）は、各成分が溶融 していれば特に限定はないが、通常 160〜350°C、好ましくは 200〜300°Cである。 また、各成分の混練順序および方法は、特に限定されるものではない。減圧混練す る事によって、重合体中の未反応成分、分解物を除去することも可能である。  [0164] The melt kneading temperature of each component (for example, cylinder temperature in the case of an extruder) is not particularly limited as long as each component is melted, but is usually 160 to 350 ° C, preferably 200 to 300 ° C. . The kneading order and method of each component are not particularly limited. It is also possible to remove unreacted components and decomposition products in the polymer by kneading under reduced pressure.
[0165] (用途）  [0165] (Use)
本発明に係る榭脂組成物は種々の用途に使用でき、例えば以下の用途に使用で きる。  The resin composition according to the present invention can be used in various applications, for example, in the following applications.
( 1)フィルムおよびシート  (1) Film and sheet
本発明に係る榭脂組成物カゝらなるフィルムおよびシートは、柔軟性、透明性、粘着 性、防曇性、耐熱性、分離性のいずれか〖こ優れている。  The film and sheet made of the resin composition according to the present invention are excellent in any one of flexibility, transparency, adhesiveness, antifogging property, heat resistance and separability.
(2)マイクロカプセル、 PTP包装、ケミカルバルブ、ドラッグデリバリーシステム。  (2) Microcapsules, PTP packaging, chemical valves, drug delivery systems.
(3)建材'土木用材料  (3) Building materials' materials for civil engineering
例えば、床材、床タイル、床シート、遮音シート、断熱パネル、防振材、化粧シート、 巾木、アスファルト改質材、ガスケット 'シーリング材、ルーフイングシート、止水シート 等の建材'土木用榭脂および建材'土木用成形体など。 For example, floor materials, floor tiles, floor sheets, sound insulation sheets, heat insulation panels, vibration proof materials, decorative sheets, Base materials such as baseboards, asphalt modifiers, gaskets 'sealing materials, roofing sheets, waterproof sheets, etc.'
(4)自動車内外装材およびガソリンタンク  (4) Automotive interior and exterior materials and gasoline tanks
本発明に係る榭脂組成物からなる自動車内外装材、ガソリンタンクは剛性、耐衝撃 性、耐油性、耐熱性に優れる。  The automotive interior / exterior material and gasoline tank comprising the resin composition according to the present invention are excellent in rigidity, impact resistance, oil resistance and heat resistance.
(5)電気、電子部品等  (5) Electricity, electronic parts, etc.
電気絶縁材料；電子部品処理用器材；磁気記録媒体、磁気記録媒体のバインダー 、電気回路の封止材、家電用素材、電子レンジ用容器などの容器用器材、電子レン ジ用フィルム、高分子電解質基材、導電性ァロイ基材等。コネクター、ソケット、抵抗 器、リレーケース、スィッチ、コイルボビン、コンデンサー、ノ リコンケース、光ピックァ ップ、光コネクター、発振子、各種端子板、変成器、プラグ、プリント配線板、チューナ 一、スピーカー、マイクロフォン、ヘッドフォン、小型モーター、磁気ヘッドベース、パ ヮーモジュール、ハウジング、半導体、液晶ディスプレー部品、 FDDキャリッジ、 FD Dシャーシ、 HDD部品、モーターブラッシュホルダー、パラボラアンテナ、コンビユー ター関連部品などに代表される電気 ·電子部品; VTR部品、テレビ部品、アイロン、 ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、オーディオ 'レーザー ディスク (登録商標） 'コンパクトディスクなどの音声機器部品、照明部品、冷蔵庫部品 、エアコン部品、タイプライター部品、ワードプロセッサー部品などに代表される家庭 Electrical insulation materials; Equipment for processing electronic components; Magnetic recording media, binders for magnetic recording media, sealing materials for electrical circuits, materials for household appliances, containers for microwave ovens, films for electronic ranges, polymer electrolytes Base material, conductive alloy base material, etc. Connector, Socket, Resistor, Relay case, Switch, Coil bobbin, Capacitor, Noricon case, Optical pick-up, Optical connector, Oscillator, Various terminal boards, Transformer, Plug, Printed wiring board, Tuner, Speaker, Microphone , Headphones, small motors, magnetic head bases, power modules, housings, semiconductors, LCD display parts, FDD carriages, FDD chassis, HDD parts, motor brush holders, parabolic antennas, computer-related parts Electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio 'Laser Disc (registered trademark)' audio equipment parts such as compact discs, lighting parts, refrigerator parts, air conditioner parts Typewriter parts, home, a typical example of which is the word processor parts
、事務電気製品部品、オフィスコンピューター関連部品、電話機関連部品、ファタシミ リ関連部品、複写機関連部品、電磁シールド材、スピーカーコーン材、スピーカー用 振動素子等。 , Office electrical product parts, office computer-related parts, telephone-related parts, fatasiri-related parts, copier-related parts, electromagnetic shielding materials, speaker cone materials, speaker vibration elements, etc.
(6)水性ェマルジヨン  (6) Water-based emulsion
本発明に係る榭脂組成物を含む水性ェマルジヨンは、ヒートシール性に優れたポリ ォレフィン用の接着剤となり得る。  The aqueous emulsion containing the resin composition according to the present invention can be an adhesive for polyolefin having excellent heat sealing properties.
(7)塗料ベース  (7) Paint base
本発明に係る榭脂組成物を含む溶剤分散体は、溶剤に対する分散安定性に優れ 、金属や極性樹脂とポリオレフインを接着する際に良好な接着性を示す。  The solvent dispersion containing the rosin composition according to the present invention is excellent in dispersion stability with respect to the solvent, and exhibits good adhesion when adhering a metal or polar resin and polyolefin.
(8)医療'衛生用材料 不織布、不織布積層体、エレクトレット、医療用チューブ、医療用容器、輸液バッグ 、プレフィルシリンジ、注射器などの医療用品、医療用材料、人工臓器、人工筋肉、 濾過膜、食品衛生'健康用品；レトルトバッグ、鮮度保持フィルムなど。 (8) Medical 'hygiene materials Non-woven fabrics, non-woven fabric laminates, electrets, medical tubes, medical containers, infusion bags, prefilled syringes, syringes and other medical supplies, medical materials, artificial organs, artificial muscles, filtration membranes, food hygiene 'health supplies; retort bags , Freshness-keeping film, etc.
(9)雑貨類  (9) Miscellaneous goods
デスクマット、カッティングマット、定規、ペンの胴軸 ·グリップ 'キャップ、ハサミゃカツ ター等のグリップ、マグネットシート、ペンケース、ペーパーフォノレダ一、バインダー、 ラベルシール、テープ、ホワイトボード等の文房具:衣類、カーテン、シーツ、絨毯、 玄関マット、バスマット、ノ ケッ、ホース、ノ ック、プランター、エアコンや排気ファンの フィルター、食器、トレー、カップ、弁当箱、コーヒーサイフォン用ロート、メガネフレー ム、コンテナ、収納ケース、ハンガー、ロープ、洗濯ネット等の生活日用雑貨類:シュ ーズ、ゴーグル、スキー板、ラケット、ボール、テント、水中メガネ、足ヒレ、釣り竿、クー ラーボックス、レジャーシート、スポーツ用ネット等のスポーツ用品：ブロック、カード、 等の玩具:灯油缶、ドラム缶、洗剤やシャンプー等のボトル、等の容器;看板、パイ口 ン、プラスチックチェーン:等の表示類等。  Desk mats, cutting mats, rulers, pen barrel shafts, grips, grips such as caps, scissors cutters, magnetic sheets, pen cases, paper phone covers, binders, label stickers, tapes, whiteboards, and other stationery: clothing , Curtains, sheets, carpets, doormats, bath mats, knocks, hoses, knocks, planters, air conditioner and exhaust fan filters, dishes, trays, cups, lunch boxes, coffee siphon funnels, glasses frames, containers, Daily necessities such as storage cases, hangers, ropes, laundry nets: shoes, goggles, skis, rackets, balls, tents, underwater glasses, foot fins, fishing rods, cooler boxes, leisure seats, sports nets Sporting goods such as: Toys such as blocks, cards, etc .: Light Cans, drums, detergent and shampoo bottles, containers and the like; signboard, pie hole down, plastic chain: display such as such.
(10)本発明に係る榭脂組成物カゝらなる層を少なくとも 1層含む積層構造体 例えば、薬剤包装材料、衣料用包装材料、壁紙、化粧板、電気絶縁用フィルム、粘 着フィルムやテープ用基材、マーキングフィルム、金属板と他材料とのラミネート、農 業用フィルム、ラップ用フィルム、シュリンク用フィルム、プロテクト用フィルム、血漿成 分分離膜、水選択透過気化膜などの分離膜例、イオン交換膜、バッテリーセパレー タ、光学分割膜などの選択分離膜など。  (10) Laminated structure comprising at least one layer comprising the resin composition according to the present invention. For example, drug packaging material, clothing packaging material, wallpaper, decorative board, electrical insulating film, adhesive film and tape. Separation membranes such as base materials, marking films, laminates of metal plates and other materials, agricultural films, wrapping films, shrink films, protective films, plasma component separation membranes, water permselective vaporization membranes, Selective separation membranes such as ion exchange membranes, battery separators, and optical separation membranes.
[0166] 〔積層構造体〕  [Laminated structure]
次に、前記した各種用途の内、積層構造体について好ましい態様を具体的に説明 する。  Next, among the various uses described above, preferred embodiments of the laminated structure will be specifically described.
[0167] 本発明に係る積層構造体は、ォレフィン系重合体を主要な構成成分として含む層（ Ll)、  [0167] The laminated structure according to the present invention includes a layer (Ll) containing an olefin-based polymer as a main constituent,
上記榭脂組成物 (C)を含む層 (L2)、  A layer (L2) containing the above-mentioned rosin composition (C),
極性ビュル系プラスチック、芳香族ビニル系重合体、ポリエステル、ポリアミド、ポリ カーボネート、エンジニアリングプラスチック、生物由来ポリマー、熱可塑性エラストマ 一、天然製または人工繊維、および金属カゝら選ばれる少なくても 1種カゝらなる層（L3) 力 層（L1)Z層（L2)Z層（L3)の順に積層している構造を少なくても一部に有して いる。 Polar bull plastic, aromatic vinyl polymer, polyester, polyamide, polycarbonate, engineering plastic, biological polymer, thermoplastic elastomer 1. A structure consisting of at least one layer selected from natural or artificial fibers and metal fibers (L3) force layer (L1) Z layer (L2) Z layer (L3) Have at least some of them.
[0168] 本発明の好ましい態様は、ォレフィン系重合体を主要な構成成分として含む層（L1 )、ポリオレフインセグメント [S ]と、極 ¾ポリマーセグメント [S ]と力もなるォレフィン系  [0168] A preferred embodiment of the present invention is an olefin-based polymer having a layer (L1) containing an olefin-based polymer as a main component, a polyolefin segment [S], and an extreme polymer segment [S].
1 2  1 2
ブロックポリマー (A2)を含む層（L2)、極性ビニル系プラスチック、ポリエステル、ポリ アミド、ポリカーボネート、エンジニアリングプラスチック、生物由来ポリマー、熱可塑 性エラストマ一、天然製または人工繊維、および金属から選ばれる少なくても 1種から なる層（L3)力 層（LI) Z層（L2) Z層（L3)の順に積層して 、る構造を少なくても一 部に有する積層構造体である。以下、層（L1)、層（L2)及び層（L3)を構成する成分 をこの順に詳細に説明した後に、層（L1)Z層（L2)Z層（L3)の順に積層している 構造を少なくても一部に有する積層構造体について説明する。  Layer (L2) containing block polymer (A2), polar vinyl plastic, polyester, polyamide, polycarbonate, engineering plastic, bio-derived polymer, thermoplastic elastomer, natural or artificial fiber, and metal This is a laminated structure in which at least a part of the layer (L3), the force layer (LI), the Z layer (L2), and the Z layer (L3) are laminated in this order. The components constituting the layer (L1), the layer (L2), and the layer (L3) are described in detail below in this order, and then the layer (L1), the Z layer (L2), and the Z layer (L3) are stacked in this order. A laminated structure having at least a part of the structure will be described.
[0169] 層（L1) [0169] Layer (L1)
層（L1)は、ォレフィン系重合体を主要な構成成分として含む層である。なお、本発 明において、「主要」とは、全体に占める重量割合が 70重量％であることをいう。  The layer (L1) is a layer containing an olefin polymer as a main constituent component. In the present invention, “major” means that the weight proportion of the whole is 70% by weight.
[0170] 本発明に係る積層構造体に用いられるォレフィン系重合体とは、エチレンおよび炭 素原子数 3〜20の α—ォレフインから選ばれる少なくても 1種のォレフィンを用いて（ 共)重合することによって得られる重合体である。炭素原子数 3〜20の aーォレフィ ンは、直鎖状であっても分岐状であってもよぐたとえばプロピレン、 1ーブテン、 2- ブテン、 1 ペンテン、 3—メチルー 1ーブテン、 1一へキセン、 4ーメチルー 1 ペン テン、 3—メチル 1—ペンテン、 1—オタテン、 1—デセン、 1—ドデセン、 1—テトラ デセン、 1一へキサデセン、 1ーォクタデセン、 1 エイコセンなどを例示することがで きる。具体的には、ポリエチレン、ホモプロピレン、ポリ（4—メチル 1—ペンテン）、 ポリ（ 1 へキセン）等のホモポリオレフイン、エチレン'プロピレンブロック共重合体等 のブロックポリプロピレン、エチレン 'プロピレン共重合体、エチレン'ブテン共重合体 、エチレン.プロピレン.ブテン共重合体等のォレフィン系共重合体、及びこれらの二 種以上力 なる組成物等が挙げられる。なお、ォレフィン系重合体が立体規則性を 有する場合はシンジオタクチックポリオレフイン、ァイソタクチックポリオレフインの 、ず れであってもよい。また、層（L1)には、必要に応じて、ォレフィン系重合体に通常添 加される公知の添加剤、例えば、タルク、シリカ、マイ力、クレー、グラスファイバー等 の無機フィラー、染顔料、酸化防止剤、加工安定剤、耐候剤、熱安定剤、光安定剤、 核剤、滑剤、離型剤、難燃剤、帯電防止剤、着色剤、紫外線吸収剤等を含有させる ことができる。 [0170] The olefin-based polymer used in the laminated structure according to the present invention is a (co) polymerization using at least one olefin selected from ethylene and α-olefin having 3 to 20 carbon atoms. It is a polymer obtained by doing. The a-olefin having 3 to 20 carbon atoms may be linear or branched, for example, propylene, 1-butene, 2-butene, 1 pentene, 3-methyl-1-butene, 1-hexene. 4-methyl-1 pentene, 3-methyl 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 eicosene and the like. Specifically, polyethylene, homopropylene, poly (4-methyl 1-pentene), homopolyolefins such as poly (1 hexene), block polypropylene such as ethylene'propylene block copolymer, ethylene'propylene copolymer, Examples thereof include olefin copolymers such as ethylene'-butene copolymer, ethylene-propylene-butene copolymer, and compositions that have at least two of these. The olefinic polymer has stereoregularity. When it has, it may be either syndiotactic polyolefin or isotactic polyolefin. In addition, the layer (L1), if necessary, is a known additive usually added to the olefin polymer, for example, inorganic fillers such as talc, silica, my strength, clay, glass fiber, dyes and pigments, Antioxidants, processing stabilizers, weathering agents, heat stabilizers, light stabilizers, nucleating agents, lubricants, mold release agents, flame retardants, antistatic agents, coloring agents, ultraviolet absorbers, and the like can be contained.
[0171] 層（L2) [0171] Layer (L2)
層 (L2)は、層 (L1)と層 (L3)を接着するための接着層として機能する重合体層で ある。層（L2)は、ブロック（a)と、ブロック（b)とからなるォレフィン系ブロックポリマー（ A2)を含んでなる層であり、好ましくはポリオレフイン (A1)とォレフイン系ブロックポリ マー (A2)とを含んでなる榭脂組成物（C)からなる層であり、特に好ましくはポリオレ フィン (A1)とォレフイン系ブロックポリマー (A2)とから構成される榭脂組成物 (C)か らなる層である。  The layer (L2) is a polymer layer that functions as an adhesive layer for bonding the layer (L1) and the layer (L3). The layer (L2) is a layer comprising an olefin-based block polymer (A2) comprising a block (a) and a block (b), preferably a polyolefin (A1) and an olefin-based block polymer (A2). And a layer made of the resin composition (C) composed of polyolefin (A1) and an olefin-based block polymer (A2). is there.
[0172] 本発明に係る積層構造体に好ましく用いられるォレフィン系ブロックポリマー (A2) は、ブロック（a) (ポリオレフインセグメント [S ] )とブロック (b) (極 ¾ポリマーセグメント [ [0172] The olefin-based block polymer (A2) preferably used in the laminated structure according to the present invention comprises a block ( a ) (polyolefin segment [S]) and a block (b) (extra-polymer segment [
1  1
S ] )とを有するォレフィン系ブロックポリマーであり、 [S ]と [S ]との結合様式によつ S])), an olefin-based block polymer, which has a coupling mode between [S] and [S].
2 1 2 2 1 2
て、ォレフィン系ブロックポリマー（A2 )とォレフイン系ブロックポリマー（A2 )にニ大  The olefin block polymer (A2) and olefin block polymer (A2)
1 2 別される。ォレフィン系ブロックポリマー (A2 )は、下記イメージ式 (i)で表される骨格  1 2 Separated. The olefin block polymer (A2) is a skeleton represented by the following image formula (i).
1  1
を持ち、 [S ]中の炭素原子と [S ]中の炭素原子が直接結合した構造を持つブロック  A block with a structure in which the carbon atom in [S] and the carbon atom in [S] are directly bonded
1 2  1 2
ポリマーである。ォレフィン系ブロックポリマー（A2 )は、 [S ]中の炭素原子と [S ]中  It is a polymer. Olefin-based block polymer (A2) consists of carbon atoms in [S] and [S]
2 1 2 の炭素原子がヘテロ原子またはへテロ原子を含む結合基によって結合された構造（ イメージ式 (ii) )を有する。二つの構造を模式的に以下に示す。以下、ォレフィン系ブ ロックポリマー（A2 )とォレフイン系ブロックポリマー（A2 )について、主に構成要素と  It has a structure (image formula (ii)) in which 2 1 2 carbon atoms are bonded by a linking group containing a hetero atom or a hetero atom. The two structures are shown schematically below. In the following, the olefin block polymer (A2) and the olefin block polymer (A2) are mainly composed of
1 2  1 2
製法の視点力 その特徴を述べる。  Viewpoint of manufacturing method The characteristics are described below.
[S ]— [S ] · · · (!)  [S] — [S] · · · (!)
1 2  1 2
[S ] -Q - [S ] · ' · (ϋ)  [S] -Q-[S] · '· (ϋ)
1 2  1 2
(式 (ii)中、 Qはへテロ原子またはへテロ原子を含む結合基を示す。 )  (In formula (ii), Q represents a hetero atom or a linking group containing a hetero atom.)
ォレフィン ブロックポリ _マー (A2 ). ♦ポリオレフインセグメント [s ] Olefin Block Polymer (A2). ♦ Polyolefin segment [s]
1  1
ォレフィン系ブロックポリマー（A2 )においては、ポリオレフインセグメント [S ]は、化  In the polyolefin block polymer (A2), the polyolefin segment [S]
1 1 学構造式上は、ポリオレフインをノヽロゲンィ匕して得られるハロゲン変性ポリオレフイン [ S ']からハロゲンラジカルが取り除かれた化学構造式を有するセグメントであることが 1 1 In terms of the structural formula, the segment should have a chemical structural formula in which halogen radicals are removed from halogen-modified polyolefin [S '] obtained by norogenating polyolefin.
1 1
好ましい。ハロゲン変性ポリオレフイン [S，]は、通常は分子量分布（MwZMn)が 1  preferable. Halogen-modified polyolefin [S,] usually has a molecular weight distribution (MwZMn) of 1
1  1
. 5以上のポリオレフイン [S "]をハロゲン化して得られる。  Obtained by halogenating 5 or more polyolefins [S "].
1  1
[0173] ポリオレフイン [S "]は、炭素原子数が 2〜20のォレフインカ 導かれる繰返し単位  [0173] Polyolefin [S "] is a repeating unit derived from polyolefin having 2 to 20 carbon atoms.
1  1
からなるポリオレフインであり、具体的には炭素原子数が 2〜20のォレフインカ 選ば れるォレフインの単独重合体またはランダム共重合体である。このポリオレフインが立 体規則性を有する場合は、ァイソタクチックポリオレフイン、シンジオタクチックポリオレ フィンのいずれであってもよい。炭素数が 2〜20のォレフィンとしては、例えば直鎖状 または分岐状の OC—ォレフイン、環状ォレフィン、芳香族ビニル化合物を例示できる  Specifically, the polyolefin is a homopolymer or random copolymer of olefin selected from 2 to 20 carbon atoms. When this polyolefin has cubic regularity, it may be either a isotactic polyolefin or a syndiotactic polyolefin. Examples of olefins having 2 to 20 carbon atoms include linear or branched OC-olefins, cyclic olefins, and aromatic vinyl compounds.
[0174] 直鎖状の a—ォレフインとして具体的には、例えばエチレン、プロピレン、 1—ブテ ン、 2—ブテン、 1—ペンテン、 1—へキセン、 1—オタテン、 1—デセン、 1—ドデセン 、 1—テトラデセン、 1—へキサデセン、 1—ォクタデセン、 1—エイコセンなどの炭素 原子数 2〜20、好ましくは 2〜 10のものを例示できる。 [0174] Specific examples of linear a-olefin include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1- Examples thereof include dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms.
[0175] 分岐状の α—ォレフインとして具体的には、例えば 3—メチルー 1ーブテン、 4ーメ チルー 1 ペンテン、 3—メチルー 1 ペンテン、 3 ェチルー 1 ペンテン、 4,4ージ メチルー 1 ペンテン、 4ーメチルー 1一へキセン、 4,4 ジメチルー 1一へキセン、 4 ーェチルー 1一へキセン、 3 ェチルー 1一へキセンなどの炭素原子数 4〜20、好ま しくは 5〜 10のものを例示できる。  [0175] Specific examples of branched α-olefin include, for example, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4 Examples thereof include 4 to 20 carbon atoms, preferably 5 to 10 carbon atoms such as -methyl-1-1 hexene, 4,4 dimethyl-1-1 hexene, 4-ethyl-1-1 hexene, 3-ethyl-1-1 hexene.
[0176] 環状ォレフィンとしては、シクロペンテン、シクロヘプテン、ノルボルネン、 5—メチル  [0176] Cyclic olefins include cyclopentene, cycloheptene, norbornene, and 5-methyl.
2—ノルボルネン、テトラシクロドデセン、ビュルシクロへキサンなどの炭素原子数 力^〜 20、好ましくは 3〜10のものを例示できる。  Examples thereof include 2-norbornene, tetracyclododecene, burcyclohexane and the like having a carbon atom number of ˜20, preferably 3-10.
[0177] ポリオレフイン [S "]の GPC分子量プロファイルは実質的にポリオレフインセグメント  [0177] The GPC molecular weight profile of polyolefin [S "] is essentially a polyolefin segment
1  1
[S ]の GPC分子量プロファイルに同一であり、重量平均分子量（Mw)は、通常 1,00 Same as GPC molecular weight profile of [S], weight average molecular weight (Mw) is usually 1,00
1 1
0〜： L000,000、より好まし <は 5,000〜400,000、さらに好まし <は 10,000〜300,0 00の範囲にある。 0 ~: L000,000, more preferred <is 5,000-400,000, more preferred <is 10,000-300,0 It is in the range of 00.
[0178] またポリオレフイン [S "]およびポリオレフインセグメント [S ]の、 GPCで求めた分子  [0178] Molecules of polyolefin [S "] and polyolefin segment [S] determined by GPC
1 1  1 1
量分布（MwZMn)が 1〜10、好ましくは 1. 5〜8、より好ましくは 1. 6〜7、さらに好 ましくは 1. 7〜6、特に好ましくは 1. 8〜5である。  The quantity distribution (MwZMn) is from 1 to 10, preferably from 1.5 to 8, more preferably from 1.6 to 7, even more preferably from 1.7 to 6, particularly preferably from 1.8 to 5.
[0179] ポリオレフインセグメント [S ]としては、炭素数 3以上の —ォレフインを少なくとも 1 [0179] The polyolefin segment [S] contains at least 1 —olefin having 3 or more carbon atoms.
1  1
種含む単独重合体または共重合体、もしくは、エチレンと環状ォレフィンとの共重合 体が好ましい。さらに、炭素数 3以上の α—ォレフィン成分に起因する立体規則性が 認められることがより好ましぐ立体規則性が高いアイソタクティシティを示すことが特 に好ましい。このようなセグメントの中でも、ポリオレフインセグメント [S ]は DSCで測  A seed-containing homopolymer or copolymer, or a copolymer of ethylene and cyclic olefin is preferred. Furthermore, it is particularly preferable to exhibit isotacticity with high stereoregularity, more preferably the stereoregularity due to the α-olefin component having 3 or more carbon atoms. Among these segments, the polyolefin segment [S] is measured by DSC.
1  1
定した融点 (Tm)に起因する吸熱ピークが 50°C以上、好ましくは 60〜200°C、より好 ましくは 70〜180°C、特に好ましくは 100〜180°Cである結晶性ポリオレフイン残基 であることが好ましい。  A crystalline polyolefin residue having an endothermic peak of 50 ° C. or higher, preferably 60 to 200 ° C., more preferably 70 to 180 ° C., particularly preferably 100 to 180 ° C. due to a fixed melting point (Tm). It is preferably a group.
[0180] このような性質を具備する結晶性ポリオレフインは、ポリエチレンもしくは高立体規則 性を示すポリオレフインである。ポリエチレンの中でも炭素数 3以上の aーォレフイン 成分の共重合量が、 0〜： LOmol%であることが好ましぐ 0〜7mol%であることがより 好ましい。高結晶性'高立体規則性ポリオレフインの中でも、炭素数 4以上の oc一才 レフインの共重合量が 0〜： LOmol%である高立体規則性プロピレン重合体が好ましく 、炭素数 4以上の (Xーォレフインの共重合量が 0〜7mol%である高立体規則性プロ ピレン重合体が好ましぐ高立体規則性プロピレンホモポリマーが更に好まし 、。  [0180] The crystalline polyolefin having such properties is polyethylene or a polyolefin exhibiting high stereoregularity. Among polyethylene, the copolymerization amount of the a-olefin component having 3 or more carbon atoms is preferably 0 to: LOmol%, more preferably 0 to 7 mol%. Among the highly crystalline 'highly stereoregular polyolefins, highly stereoregular propylene polymers having a copolymerization amount of oc 1-year-old refin having 4 or more carbon atoms from 0 to: LOmol% are preferred. More preferred is a highly stereoregular propylene homopolymer, preferably a highly stereoregular propylene polymer having a copolymerization amount of olefins of 0 to 7 mol%.
[0181] ポリオレフインセグメント [S ]の前駆体となるポリオレフイン [S "]の製造は従来公知  [0181] Production of polyolefin [S "], which is a precursor of the polyolefin segment [S], is conventionally known
1 1  1 1
のォレフイン重合触媒の存在下に行われる。従来公知のォレフィン重合用触媒として は、 TiCl系触媒、 MgCl担持型 TiCl系触媒、クロム系触媒、メタ口セン系触媒、ボス This is carried out in the presence of an olefin polymerization catalyst. Conventionally known olefin polymerization catalysts include TiCl-based catalysts, MgCl-supported TiCl-based catalysts, chromium-based catalysts, meta-octane-based catalysts, and bosses.
3 2 4 3 2 4
トメタロセン系触媒などが挙げられ、 MgCl担持型 TiCl系触媒もしくはメタ口セン系触  To metallocene catalysts, MgCl-supported TiCl catalysts or metallocene catalysts
2 4  twenty four
媒を用いて製造されて 、ることが好ま 、。  It is preferable to be manufactured using a medium.
[0182] ハロゲン変性ポリオレフイン [S ']は、上記したポリオレフイン [S "]を公知のハロゲ [0182] The halogen-modified polyolefin [S '] is a known halogenated polyolefin [S "].
1 1  1 1
ン化剤を用いるハロゲン化方法によって製造することができる。ハロゲン化剤としては 、上記ハロゲン変性ポリオレフイン (a' )の製造方法で例示したィ匕合物が挙げられる。 なお、ハロゲン化剤との反応においては、反応を促進するために必要に応じて、過酸 化べンゾィル、過酸化ジー tert ブチル、過酸化ラウロイル、過酸化ァセチル、過酸 化ジイソプロピルジカーボネート、タメンヒドロペルォキシド、 tert ブチルヒドロペルォ キシド、ジクミルペルォキシド、ァゾビスイソブチ口-トリル、ァゾビス 2,4 ジメチル バレロ-トリル、ァゾビスシクロへキサンカルボ-トリル、ァゾビスイソ酪酸ジメチルラジ カルなどに代表される開始剤を添加することもできる。このようにして得られたハロゲ ン変性ポリオレフイン [S ']のハロゲン含有率は、通常 0. 01〜70重量％、好ましくは It can be produced by a halogenation method using an oxidizing agent. Examples of the halogenating agent include the compounds exemplified in the method for producing the halogen-modified polyolefin (a ′). In the reaction with the halogenating agent, a peracid is used as necessary to accelerate the reaction. Benzyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, acetyl peroxide, diisopropyl dicarbonate, tamen hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, azobisisobutyoxy-tolyl, An initiator typified by azobis 2,4 dimethyl valero-tolyl, azobiscyclohexanecarbo-tolyl, azobisisobutyric acid dimethyl radical and the like can also be added. The halogen content of the halogen-modified polyolefin [S ′] thus obtained is usually 0.01 to 70% by weight, preferably
1  1
0. 02〜50重量％、さらに好ましくは 0. 05〜30重量％である。なお、ハロゲン変性 ポリオレフイン [S ']中に存在するハロゲン原子含有量は、例えば元素分析やイオン  It is 0.02 to 50% by weight, more preferably 0.05 to 30% by weight. The halogen atom content present in the halogen-modified polyolefin [S ′] is, for example, elemental analysis or ion
1  1
クロマトグラフィーなどの方法により測定することができる。また、ハロゲン変性ポリオレ フィン [S ']中に存在する炭素 炭素二重結合含有量は、例えば赤外分光法ゃ核磁 It can be measured by a method such as chromatography. The carbon-carbon double bond content present in the halogen-modified polyolefin [S ′] is, for example, determined by infrared spectroscopy or nuclear magnetic field.
1 1
気共鳴法 (NMR)などの方法により測定することができる。さらに、炭素-炭素二重 結合のァリル位に存在するハロゲン原子については、例えば NMRにより確認および 定量することができる。ァリル位に存在するハロゲン原子確認の具体例としては、例 えば臭素化ポリプロピレンの重水素化オルトジクロロベンゼンを溶媒に用いたプロトン It can be measured by a method such as gas resonance (NMR). Furthermore, the halogen atom present at the aryl position of the carbon-carbon double bond can be confirmed and quantified by, for example, NMR. Specific examples of the confirmation of the halogen atom present at the aryl position include, for example, protons using deuterated orthodichlorobenzene of brominated polypropylene as a solvent.
NMRにおいて、炭素 炭素二重結合に基づくシグナルは通常 δ 4. 5〜6. Oppm の範囲に観測され、臭素原子が結合したァリル位のメチレン基およびメチン基は通常 δ 3. 5〜4. 5ppmに観測される。ァリル位以外のメチレン基およびメチン基に臭素 原子が導入された場合のシグナル位置は通常、 δ 3. 0〜3. 5ppmであるため、臭素 原子がァリル位に存在しているかそうでないかは容易に識別可能である。力！]えて、例 えばプロトン プロトン二次元 NMR (HH COSY)を用 、ることにより、上記炭素 炭素二重結合に基づくシグナルと、臭素原子が結合したメチレン基およびメチン基の シグナルとの相関関係を確認することも可能である。 In NMR, a signal based on a carbon-carbon double bond is usually observed in the range of δ 4.5 to 6. Oppm, and a methylene group and a methine group at the aryl position to which a bromine atom is bonded are usually δ 3.5 to 4.5 ppm. Observed at. The signal position when a bromine atom is introduced into a methylene group and a methine group other than the aryl position is usually δ 3.0 to 3.5 ppm, so it is easy to determine whether the bromine atom is present at the aryl position or not. Can be identified. Power! For example, by using proton proton two-dimensional NMR (HH COZY), the correlation between the signal based on the carbon-carbon double bond and the signals of the methylene group and methine group to which the bromine atom is bonded was confirmed. It is also possible to do.
[0183] このようにして得られるハロゲン変性ポリオレフイン [S ']は、重合体主鎖の末端に [0183] The halogen-modified polyolefin [S '] thus obtained is attached to the end of the polymer main chain.
1  1
前記一般式 (I)〜 (III)で表される構成単位力 選ばれる少なくとも一つの構成単位 が接続された構造、および Zまたは重合体主鎖中に前記一般式 (IV)〜 (VII)で表さ れる構成単位カゝら選ばれる少なくとも一つの構成単位が挿入された構造を有する。  Structural unit forces represented by the general formulas (I) to (III): a structure in which at least one selected structural unit is connected, and Z or the general formulas (IV) to (VII) in the polymer main chain. It has a structure in which at least one structural unit selected from the structural unit represented is inserted.
[0184] ハロゲン変性ポリオレフイン [S ']においては、炭素 炭素二重結合の α位に存在  [0184] In halogen-modified polyolefin [S '], exists in the α-position of the carbon-carbon double bond
1  1
する炭素 ハロゲン結合、あるいは一つの炭素原子上に複数のハロゲンが付加した 構造を開始剤構造として利用し、ヘテロ元素含有重合性モノマーを重合することによ つて極性ポリマーセグメント [S ]を導入することができる。流動性と接着性能の観点 Carbon, halogen bond, or multiple halogens added on one carbon atom The polar polymer segment [S] can be introduced by using the structure as an initiator structure and polymerizing a hetero-element-containing polymerizable monomer. Viewpoint of fluidity and adhesive performance
2  2
力も平均ハロゲン原子導入本数としては、 0. 3〜 10本が好ましぐ 0. 5〜8本がより 好ましく、 0. 7〜5本がさらに好ましい。  The average number of introduced halogen atoms is preferably 0.3 to 10, more preferably 0.5 to 8, and even more preferably 0.7 to 5.
[0185] ポリマー 1本鎖あたりの平均ハロゲン導入数 Nは以下のように求めた。 GPCより求め られる数平均分子量を Mn、 iH— NMRから求められる、導入モノマーの平均分子量 を Fw(ave)、ハロゲン基の全モノマー連鎖単位に対するモル含有量を、 n (mol%)と したとき、ポリマー 1本鎖あたりの平均ハロゲン導入数 N (本 Z鎖）は次式により求めら れる。 [0185] The average number N of halogens introduced per polymer chain was determined as follows. The number average molecular weight obtained from GPC is Mn, the average molecular weight of the introduced monomer is Fw (ave), and the molar content of the halogen group with respect to all monomer chain units is n (mol%). The average number N of halogens introduced per polymer chain (the Z chain) can be obtained from the following equation.
[0186] N = n X Mn/ [Fw(ave) X 100]  [0186] N = n X Mn / [Fw (ave) X 100]
♦極性ポリマーセグメント [S ]  ♦ Polar polymer segment [S]
2  2
ォレフィン系ブロックポリマー (A2)を構成する極性ポリマーセグメント [S ]とは、ラジ  The polar polymer segment [S] constituting the olefin block polymer (A2)
2 カル重合性単量体から選ばれる 1種以上のモノマーの単独重合体または共重合体 である。本発明で用いられるラジカル重合性単量体としては、具体的には、上記プロ ック (b)の説明中に例示したラジカル重合性単量体と同様のものが挙げられる。これ らの有機化合物は、単独で、または 2種類以上を組み合わせて使用しても構わない。  2 A homopolymer or copolymer of one or more monomers selected from calpolymerizable monomers. Specific examples of the radically polymerizable monomer used in the present invention include those similar to the radically polymerizable monomer exemplified in the description of the above-described block (b). These organic compounds may be used alone or in combination of two or more.
[0187] 極性ポリマーセグメント [S ]としては、（メタ)アクリル酸およびその誘導体、（メタ）ァ [0187] The polar polymer segment [S] includes (meth) acrylic acid and its derivatives, (meth)
2  2
クリロ-トリル、スチレンおよびその誘導体、（メタ)アクリルアミドおよびその誘導体、マ レイン酸およびその誘導体、マレイミドおよびその誘導体、ビュルエステル類、共役ジ ェン類、ハロゲン含有ォレフィン類力 選ばれる一種あるいは二種以上の単量体を（ 共)重合して得られる重合体が好ましぐ（メタ)アクリル酸およびその誘導体、（メタ)ァ クリロ-トリル、スチレンおよびその誘導体力 選ばれる 1種あるいは 2種以上の単量 体を (共)重合して得られる重合体がより好ましぐ（メタ）アクリル酸エステル、スチレン 、（メタ）アクリルアミド、（メタ）アクリロニトリル、（メタ)アクリル酸の単独重合体および共 重合体が更に好ましく用いることができる。  Chryro-tolyl, styrene and its derivatives, (meth) acrylamide and its derivatives, maleic acid and its derivatives, maleimide and its derivatives, buresters, conjugated diene, halogen-containing olefins Polymers obtained by (co) polymerizing the above monomers are preferred (meth) acrylic acid and its derivatives, (meth) acrylo-tolyl, styrene and its derivatives. (Meth) acrylic acid esters, styrene, (meth) acrylamide, (meth) acrylonitrile, (meth) acrylic acid homopolymers and copolymers A polymer can be more preferably used.
[0188] 本発明においてォレフィン系ブロックポリマー（A2 )中の極性ポリマーセグメント [S [0188] In the present invention, the polar polymer segment in the olefin block polymer (A2) [S
1 2 1 2
]は、数平均分子量力 1,000〜500,000であること力 S好ましく、 3,000〜300,000で あることがより好ましい。分子量力 Sこの範囲より高いときには流動性が低下し、成形性 が悪化する。この範囲より低いときには接着性能が低下する。 ] Has a number average molecular weight force of 1,000 to 500,000, preferably S, and more preferably 3,000 to 300,000. Molecular weight force S When higher than this range, fluidity decreases and moldability Gets worse. When it is lower than this range, the adhesive performance is lowered.
[0189] 本発明の積層構造体においては、ォレフィン系ブロックポリマー（A2 )中の極性ポ  [0189] In the laminated structure of the present invention, the polar polymer in the olefin-based block polymer (A2) is used.
1  1
リマーセグメント [S ]は、層（L1)と層（L2)の接着力を向上させ可塑剤保持性を良く  The remer segment [S] improves the adhesion between the layers (L1) and (L2) and improves the plasticizer retention.
2  2
する観点から、あるいは層（L2)中のォレフィン系ブロックポリマー（A2)以外の成分 への溶解性'分散性が良好となるという理由によって、溶解度パラメーターが 18〜25 (jZm)の範囲であり、好ましくは 18〜24 (jZm)の範囲であり、より好ましくは 18. 2 〜22 (jZm)の範囲であり、さらに好ましくは 18. 4〜20 (JZm)の範囲であるへテロ 元素含有の重合性モノマーの重合体であることが好ましい。  The solubility parameter is in the range of 18 to 25 (jZm), because of good solubility or dispersibility in components other than the olefin-based block polymer (A2) in the layer (L2), Preferably it is in the range of 18-24 (jZm), more preferably in the range of 18.2-22 (jZm), and even more preferably in the range of 18.4-20 (JZm). It is preferably a polymer of a functional monomer.
[0190] 極性ポリマーセグメント [S ]の溶解度パラメータ一は極性ポリマーセグメント [S ]を [0190] The solubility parameter of the polar polymer segment [S] is the polar polymer segment [S]
2 2 構成する共重合体の組成から計算できる。なお、本発明において溶解度パラメータ 一は、極性ポリマーセグメント [S ]の組成を Million Zillion Software, Inc.製 CHEOPS  2 2 Calculated from the composition of the constituent copolymers. In the present invention, the solubility parameter 1 is the CHEOPS manufactured by Million Zillion Software, Inc.
2  2
Ver. 4.0に人力し、計算した。  Calculated by manpower to Ver. 4.0.
[0191] 榭脂組成物（C)においては、室温クロ口ホルム不溶成分を1 H— NMRで分析するこ とによって、極性ポリマーセグメント [S ]の組成を計算することが出来る。 [0191] In the rosin composition (C), the composition of the polar polymer segment [S] can be calculated by analyzing the room-temperature chloroform-insoluble component by 1 H-NMR.
2  2
[0192] ォレフィン系ブロックポリマー（A2)中の極†¾ポリマーセグメント [S ]はイソシァネー  [0192] The polymer segment [S] in the olefin block polymer (A2) is isocyanate
2  2
ト基、カルボキシル基、アミド基、ヒドロキシル基、酸無水物基、エポキシ基、ォキサゾ リン基、マレイミド基、アミン基、イミン基およびエーテル基力 なる群力 選ばれる少 なくとも 1種のラジカル重合性単量体を含有していることが接着力の視点力 好まし い。  Group, carboxyl group, amide group, hydroxyl group, acid anhydride group, epoxy group, oxazoline group, maleimide group, amine group, imine group, and ether group group power of at least one kind selected It is preferable to have a monomer from the viewpoint of adhesive strength.
[0193] ォレフィン系ブロックポリマー（A2 )中の極性ポリマーセグメント [S ]は、接着力の  [0193] The polar polymer segment [S] in the olefin block polymer (A2)
1 2  1 2
点で、示差走査型熱量計 (DSC)で測定したガラス転移温度 (Tg)が、 25°C以下が 好ましぐより好ましくは 60〜25°C、さらに好ましくは 50〜20°Cである。  In this respect, the glass transition temperature (Tg) measured with a differential scanning calorimeter (DSC) is preferably 25 ° C. or less, more preferably 60 to 25 ° C., and even more preferably 50 to 20 ° C.
[0194] カルボキシル基を含有するラジカル重合性単量体としては、アクリル酸、メタクリル 酸、マレイン酸、フマル酸、テトラヒドロフタル酸、ィタコン酸、シトラコン酸、クロトン酸、 イソクロトン酸、ノルボルネンジカルボン酸、ビシクロ [2.2.1]ヘプトー 2 ェン一 5,6 ジカルボン酸などが挙げられ、カルボキシル基含有ラジカル重合性単量体の誘導 体としては、これらの酸無水物およびこれらの酸ノヽライド、アミド、イミド、エステルなど の誘導体が挙げられる。具体的には、塩化マレニル、マレ二ルイミド、無水マレイン酸 、無水ィタコン酸、無水シトラコン酸、テトラヒドロ無水フタル酸、ビシクロ [2.2.1]ヘプ トー 2 ェン—5, 6 ジカルボン酸無水物、マレイン酸ジメチル、マレイン酸モノメチ ル、マレイン酸ジェチル、フマル酸ジェチル、ィタコン酸ジメチル、シトラコン酸ジェチ ル、テトラヒドロフタル酸ジメチル、ビシクロ [2.2.1]ヘプトー 2 ェン 5, 6 ジカルボ ン酸ジメチル、ヒドロキシェチル (メタ）アタリレート、ヒドロキシプロピル (メタ）アタリレー ト、グリシジル (メタ)アタリレート、メタクリル酸アミノエチル、メチル (メタ)アタリレート、 ェチル (メタ）アタリレート、メタクリル酸アミノプロピルなどを挙げることができる。 [0194] Radical polymerizable monomers containing a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2.2.1] Hepto-2-ene-1,6 dicarboxylic acid and the like, and examples of the derivative of the carboxyl group-containing radical polymerizable monomer include these acid anhydrides and acid anhydrides, amides, imides thereof. And derivatives such as esters. Specifically, maleyl chloride, maleilimide, maleic anhydride , Itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6 dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, jetyl maleate, jetyl fumarate , Dimethyl itaconate, dimethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2.2.1] hept-2-ene 5,6 dimethyl dicarbonate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate Examples thereof include glycidyl (meth) acrylate, aminoethyl methacrylate, methyl (meth) acrylate, ethyl (meth) acrylate and aminopropyl methacrylate.
[0195] ヒドロキシル基を含有するラジカル重合性単量体としては、ヒドロキシェチル (メタ）ァ タリレート、 2 ヒドロキシプロピル (メタ）アタリレート、 3 ヒドロキシプロピル (メタ）ァク リレート、 2 ヒドロキシ一 3 フエノキシ一プロピノレ (メタ）アタリレート、 3 クロ口一 2— ヒドロキシプロピル (メタ）アタリレート、グリセリンモノ（メタ）アタリレート、ペンタエリスリト ールモノ (メタ）アタリレート、トリメチロールプロパンモノ (メタ）アタリレート、テトラメチロ ールェタンモノ（メタ）アタリレート、ブタンジオールモノ（メタ）アタリレート、ポリエチレ ングリコールモノ（メタ）アタリレート、 2- (6—ヒドロキシへキサノィルォキシ）ェチルァ タリレートなどの（メタ）アクリル酸エステル； 10—ゥンデセン— 1—オール、 1—ォクテ ンー3 オール、 2 メタノールノルボルネン、ヒドロキシスチレン、ヒドロキシェチルビ -ルエーテル、ヒドロキシブチルビ-ルエーテル、 N—メチロールアクリルアミド、 2— ( メタ）ァクロィルォキシェチルアシッドフォスフェート、グリセリンモノアリルエーテル、ァ リルアルコール、ァリロキシエタノール、 2 ブテン 1,4ージオール、グリセリンモノア ルコールなどが挙げられる。 [0195] Examples of the radical polymerizable monomer containing a hydroxyl group include hydroxyethyl (meth) acrylate, 2 hydroxypropyl (meth) acrylate, 3 hydroxypropyl (meth) acrylate, 2 hydroxy 1-3 phenoxy. 1 propynole (meth) acrylate, 3 black mouth 2— hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylol propane mono (meth) acrylate, (Meth) acrylic acid esters such as tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecene — 1 All, 1-octen-3ol, 2 Methanol norbornene, Hydroxystyrene, Hydroxyethyl vinyl ether, Hydroxybutyl vinyl ether, N-Methylol acrylamide, 2- (Meth) acryloxychhetyl acid phosphate, Examples include glycerin monoallyl ether, aryl alcohol, aryloxyethanol, 2-butene 1,4-diol, and glycerin monoalcohol.
[0196] ォキサゾリン基、マレイミド基、アミン基、イミン基力 選ばれる少なくとも 1種の基を 含有するラジカル重合性単量体としては、例えばエチレン性二重結合とアミノ基を有 するアミノ基含有エチレン性不飽和化合物が挙げられ、アミノ基含有エチレン性不飽 和化合物としては、具体的には、（メタ)アクリル酸アミノエチル、（メタ)アクリル酸プロ ピルアミノエチル、メタクリル酸ジメチルアミノエチル、（メタ）アクリル酸ァミノプロピル、 メタクリル酸フエ-ルアミノエチル、メタクリル酸シクロへキシルアミノエチルなどのァク リル酸またはメタクリル酸のアルキルエステル系誘導体類； N ビ-ルジェチルァミン 、 N ァセチルビ-ルァミンなどのビュルアミン系誘導体類；ァリルアミン、メタクリルァ ミン、 N メチルアクリルァミン、 Ν,Ν ジメチルアクリルアミド、 Ν,Ν ジメチルァミノ プロピルアクリルアミドなどのァリルアミン系誘導体；アクリルアミド、 Ν—メチルアクリル アミドなどのアクリルアミド系誘導体； ρ -アミノスチレンなどのアミノスチレン類； 6—ァ ミノへキシルコハク酸イミド、 2—アミノエチルコハク酸イミドなどが用いられる。 [0196] As the radical polymerizable monomer containing at least one kind of group selected from oxazoline group, maleimide group, amine group, imine group power, for example, amino group-containing ethylene having ethylenic double bond and amino group Specific examples of the amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, ( Alkyl ester derivatives of acrylic acid or methacrylic acid such as meth) acryloyl acrylate, phenolaminoethyl methacrylate, cyclohexylaminoethyl methacrylate; and buramine derivatives such as N-vinyljetylamine and N-acetylbutylamine. ; Arylamine, methacrylate Minary, N-methylacrylamine, Ν, ジ メ チ ル dimethylacrylamide, Ν, Ν dimethylamine Derivatives such as dimethylacrylamide; Acrylamide derivatives such as acrylamide and Ν-methylacrylamide; Aminostyrenes such as ρ-aminostyrene; 6 —Aminohexyl succinimide, 2-aminoethyl succinimide, etc. are used.
[0197] エポキシ基を含有するラジカル重合性単量体は、 1分子中に重合可能な不飽和結 合およびエポキシ基を少なくとも 1個以上有するモノマーであり、このようなエポキシ 基含有ラジカル重合性単量体として具体的には、グリシジルアタリレート、グリシジル メタタリレート、マレイン酸のモノおよびジグリシジルエステル、フマル酸のモノおよび ジグリシジルエステル、クロトン酸のモノおよびジグリシジルエステル、テトラヒドロフタ ル酸のモノおよびジグリシジルエステル、ィタコン酸のモノおよびグリシジルエステル 、ブテントリカルボン酸のモノおよびジグリシジルエステル、シトラコン酸のモノおよび ジグリシジノレエステノレ、エンド シス -ビシクロ [2.2.1]ヘプトー 5 ェン一 2, 3 ジカ ルボン酸（ナジック酸™)のモノおよびジグリシジルエステル、エンド シス ビシクロ [ 2.2.1]ヘプト 5 ェンー 2 メチル - 2,3-ジカルボン酸 (メチルナジック酸™)のモ ノおよびジグリシジルエステル、ァリルコハク酸のモノおよびグリシジルエステルなどの ジカルボン酸モノおよびアルキルグリシジルエステル（モノグリシジルエステルの場合 は、アルキル基の炭素原子数は 1〜12。）、 ρ—スチレンカルボン酸のアルキルグリシ ジルエステル、ァリルグリシジルエーテル、 2—メチルァリルグリシジルエーテル、スチ レン ρ グリシジルエーテル、 3,4 エポキシー1ーブテン、 3,4 エポキシー3—メ チルー 1ーブテン、 3, 4 エポキシ 1 ペンテン、 3,4 エポキシ 3—メチルー 1 ペンテン、 5,6 エポキシ 1一へキセン、ビニルシクロへキセンモノォキシドなど が挙げられる。 [0197] A radical polymerizable monomer containing an epoxy group is a monomer having at least one unsaturated bond and epoxy group polymerizable in one molecule. Such an epoxy group-containing radical polymerizable monomer. Specific examples of the mer include glycidyl atylate, glycidyl metatalylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, and mono and di of tetrahydrophthalic acid. Glycidyl esters, mono- and glycidyl esters of itaconic acid, mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidino-reestenoles of citraconic acid, endo-cis-bicyclo [2.2.1] hept-5-one 2,3 dica Mono and rubonic acid (Nadic Acid ™) Diglycidyl esters, endo-cis bicyclo [2.2.1] hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid ™) mono and diglycidyl esters, allylic succinic acid mono and glycidyl mono And alkyl glycidyl ester (in the case of monoglycidyl ester, the alkyl group has 1 to 12 carbon atoms), ρ-alkyl glycidyl ester of styrene carboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene Len ρ Glycidyl ether, 3,4 Epoxy 1-butene, 3,4 Epoxy 3-methyl-1-butene, 3, 4 Epoxy 1 pentene, 3,4 Epoxy 3-methyl-1-pentene, 5,6 Epoxy 1 Hexene, Vinylcyclo Examples include hexene monooxide.
[0198] ォレフィン系ブロックポリマー（Α2 )は、上記ハロゲン変性ポリオレフイン [S ']をマク  [0198] The olefin-based block polymer (Α2) is made up of the above halogen-modified polyolefin [S '].
1 1 口開始剤として、前記したラジカル重合性単量体力 選ばれる一種以上のモノマーを ラジカル共重合することにより製造される。ラジカル共重合方法は特に制限されるも のではないが、通常は原子移動ラジカル共重合法が好んで用いられる。なお、本発 明のマクロ開始剤とは、原子移動ラジカル重合の開始能を有する重合体であり、分 子鎖中に原子移動ラジカル重合の開始点となりうる部位を有する重合体を表す。 [0199] 本発明における原子移動ラジカル重合とは、リビングラジカル重合の一つであり、 有機ハロゲンィ匕物又はハロゲン化スルホ二ルイ匕合物を開始剤、遷移金属を中心金 属とする金属錯体を触媒としてラジカル重合性単量体をラジカル重合する方法であ る。（例えば、 Matyjaszewskiら、 Chem. Rev., 101, 2921 (2001)、 WO96/30421号パン フレット、 W097/18247号パンフレット、 WO98/01480号パンフレット、 WO98/40415号 パンフレット、 WO00/156795号パンフレット等に関連情報が開示されている。）用いら れる開始剤としては、例えば有機ハロゲンィ匕物やハロゲン化スルホ-ルイ匕合物が挙 げられるが、特に炭素 炭素二重結合または炭素 酸素二重結合の α位に存在す る炭素 ハロゲン結合、あるいは一つの炭素原子上に複数のハロゲンが付加した構 造が開始剤構造として好適である。ハロゲン変性ポリオレフイン [S ']においては、炭 1 1 It is produced by radical copolymerizing one or more monomers selected from the radically polymerizable monomer force described above as a single-mouth initiator. The radical copolymerization method is not particularly limited, but usually the atom transfer radical copolymerization method is preferably used. The macroinitiator of the present invention is a polymer having the ability of initiating atom transfer radical polymerization, and represents a polymer having a site that can be the starting point of atom transfer radical polymerization in the molecular chain. [0199] Atom transfer radical polymerization in the present invention is one of living radical polymerizations, in which a metal complex having an organic halide or halogenated sulfone compound as an initiator and a transition metal as a central metal is used. This is a method of radical polymerization of a radical polymerizable monomer as a catalyst. (For example, Matyjaszewski et al., Chem. Rev., 101, 2921 (2001), WO96 / 30421 pamphlet, W097 / 18247 pamphlet, WO98 / 01480 pamphlet, WO98 / 40415 pamphlet, WO00 / 156795 pamphlet, etc. Related information is disclosed.) Initiators used include, for example, organic halides and halogenated sulfo-ruly compounds, especially carbon-carbon double bonds or carbon-oxygen double bonds. A structure in which a carbon-halogen bond at the α-position or a plurality of halogen atoms are added on one carbon atom is suitable as the initiator structure. In the halogen-modified polyolefin [S ']
1  1
素 炭素二重結合の α位に存在する炭素 ハロゲン結合、あるいは一つの炭素原 子上に複数のハロゲンが付加した構造を開始剤構造として利用することができる。  A carbon-halogen bond present at the α-position of a carbon-carbon double bond, or a structure in which a plurality of halogens are added on one carbon atom can be used as an initiator structure.
[0200] ハロゲン変性ポリオレフイン [S ']をマクロ開始剤とするォレフィン系ブロックポリマー [0200] Olefin-based block polymer using halogen-modified polyolefin [S '] as macroinitiator
1  1
(Α2 )の製造方法は、基本的には上記変性ポリオレフイン [S ']の存在下、遷移金属 The production method of (Α2) is basically the transition metal in the presence of the modified polyolefin [S ′].
1 1 1 1
を中心金属とする金属錯体を重合触媒としてラジカル重合性単量体を原子移動ラジ カル重合させるものである。  A radically polymerizable monomer is atom-transferred radically polymerized using a metal complex having a central metal as a polymerization catalyst.
[0201] 重合触媒として用いられる遷移金属錯体としては特に限定されないが、好ましくは 周期表第 7族、 8族、 9族、 10族、または 11族元素を中心金属とする金属錯体である 。更に好ましいものとして、 0価の銅、 1価の銅、 2価のルテニウム、 2価の鉄又は 2価 のニッケルの錯体が挙げられる。なかでも、銅の錯体が好ましい。 1価の銅化合物を 具体的に例示するならば、塩化第一銅、臭化第一銅、ヨウ化第一銅、シアンィ匕第一 銅、酸化第一銅、過塩素酸第一銅等である。銅化合物を用いる場合、触媒活性を高 めるために 2,2 '—ビビリジル、もしくはその誘導体、 1,10—フエナント口リン若しくはそ の誘導体、又はテトラメチルエチレンジァミン、ペンタメチルジェチレントリァミン若しく はへキサメチルトリス（2—アミノエチル)ァミン等のポリアミン等が配位子として添加さ れる。また、 2価の塩化ルテニウムのトリストリフエ-ルホスフィン錯体 (RuCl (PPh ) )  [0201] The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a metal complex having a group 7 element, group 8, group 9, group 10, or group 11 element of the periodic table as a central metal. Further preferred are a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cyanide cuprous, cuprous oxide, cuprous perchlorate, etc. is there. In the case of using a copper compound, 2,2′-bibilidyl or a derivative thereof, 1,10-phenantine phosphorus or a derivative thereof, or tetramethylethylenediamine or pentamethylethylenediamine is used to increase the catalytic activity. Minamine or polyamines such as hexamethyltris (2-aminoethyl) amine are added as ligands. Also, tristriphenylphosphine complex of divalent ruthenium chloride (RuCl (PPh))
2 3 3 も触媒として好適である。ルテニウム化合物を触媒として用いる場合は、活性化剤と してアルミニウムアルコキシド類が添加される。更に、 2価の鉄のビストリフエ-ルホス フィン錯体（FeCl (PPh ) )、 2価のニッケルのビストリフ ニルホスフィン錯体（NiCl (P 2 3 3 is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, divalent iron bistriphenylphosphine Fin complexes (FeCl (PPh)), divalent nickel bistriphenylphosphine complexes (NiCl (P
2 3 3 2 2 3 3 2
Ph ) )、及び、 2価のニッケルのビストリブチルホスフィン錯体（NiBr (PBu ) )も、触媒Ph)) and bivalent nickel bistributylphosphine complex (NiBr (PBu))
3 2 2 3 2 として好適である。 3 2 2 3 2 is preferred.
[0202] 原子移動ラジカル重合方法は特に限定されず、塊状重合、溶液重合、懸濁重合、 乳化重合、塊状 ·懸濁重合などを適用することができる。ラジカル重合において使用 できる溶媒としては、反応を阻害しな 、ものであれば何れでも使用することができるが 、例えば、具体例として、ベンゼン、トルエンおよびキシレン等の芳香族炭化水素系 溶媒、ペンタン、へキサン、ヘプタン、オクタン、ノナンおよびデカン等の脂肪族炭化 水素系溶媒、シクロへキサン、メチルシクロへキサンおよびデカヒドロナフタレンのよう な脂環式炭化水素系溶媒、クロ口ベンゼン、ジクロロベンゼン、トリクロ口ベンゼン、塩 ィ匕メチレン、クロ口ホルム、四塩ィ匕炭素およびテトラクロルエチレン等の塩素化炭化水 素系溶媒、メタノール、エタノール、 n—プロパノール、 。一プロパノール、 n—ブタノ ール、 sec—ブタノールおよび tert—ブタノール等のアルコール系溶媒、アセトン、メ チルェチルケトンおよびメチルイソブチルケトン等のケトン系溶媒；酢酸ェチルおよび ジメチルフタレート等のエステル系溶媒、ジメチルエーテル、ジェチルエーテル、ジ —n—ァミルエーテル、テトラヒドロフランおよびジォキシァ-ソールのようなエーテル 系溶媒等をあげることができる。また、水を溶媒として、懸濁重合、乳化重合すること もできる。これらの溶媒は、単独でもまたは 2種以上を混合して使用してもよい。また、 これらの溶媒の使用によって、反応液が均一相となることが好ましいが、不均一な複 数の相となっても構わない。 [0202] The atom transfer radical polymerization method is not particularly limited, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, bulk / suspension polymerization, and the like can be applied. As the solvent that can be used in radical polymerization, any solvent that does not inhibit the reaction can be used. For example, specific examples include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, pentane, Aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane and decane, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene, black benzene, dichlorobenzene, trichlorolip Chlorinated hydrocarbon solvents such as benzene, chloride methylene, chloroform, tetrasalt carbon and tetrachloroethylene, methanol, ethanol, n -propanol. Alcohol solvents such as monopropanol, n -butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, And ether solvents such as tilether, di-n-amyl ether, tetrahydrofuran and dioxy-sol. In addition, suspension polymerization or emulsion polymerization can be performed using water as a solvent. These solvents may be used alone or in combination of two or more. In addition, it is preferable that the reaction liquid becomes a homogeneous phase by using these solvents, but it may be a heterogeneous plural phase.
[0203] 反応温度はラジカル重合反応が進行する温度であれば何れでも構わず、所望する 重合体の重合度、使用するラジカル重合開始剤および溶媒の種類や量によって一 様ではないが、通常、— 100°C〜250°Cである。好ましくは— 50°C〜180°Cであり、 更に好ましくは 0°C〜160°Cである。反応は場合によって減圧、常圧または加圧の何 れでも実施できる。上記重合反応は、窒素やアルゴン等の不活性ガス雰囲気下で行 うことが好ましい。 [0203] The reaction temperature may be any temperature as long as the radical polymerization reaction proceeds, and is not uniform depending on the desired degree of polymerization of the polymer, the type and amount of the radical polymerization initiator and solvent to be used. — 100 ° C ~ 250 ° C. Preferably, it is −50 ° C. to 180 ° C., more preferably 0 ° C. to 160 ° C. In some cases, the reaction can be carried out under reduced pressure, normal pressure or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
[0204] 上記の方法により生成したォレフィン系ブロックポリマー (A2 )は、重合に用いた溶  [0204] The olefin-based block polymer (A2) produced by the above method is used for the solution used in the polymerization.
1  1
媒ゃ未反応のモノマーの留去あるいは非溶媒による再沈殿などの公知の方法を用 いること〖こより単離される。更に、得られたポリマーを、ソックスレー抽出装置を用い、 アセトンや THFなどの極性溶媒で処理することで、副生したホモラジカル重合体を除 去することが可能である。 Use known methods such as evaporation of unreacted monomer or reprecipitation with non-solvent. It is isolated from the octopus. Furthermore, by treating the obtained polymer with a polar solvent such as acetone or THF using a Soxhlet extraction apparatus, it is possible to remove the by-product homoradical polymer.
[0205] ォレフィン ブロックポリ _マー (A2 ). [0205] Olefin Block Polymer (A2).
2  2
前記イメージ式 (ii)で表されるォレフィン系ブロックポリマー（A2 )においては、ポリ  In the olefin block polymer (A2) represented by the image formula (ii),
2  2
ォレフィンセグメント [S ]と極性ポリマーセグメント [S ]の構成成分は、各々既述した  The components of the olefin segment [S] and the polar polymer segment [S] have been described above.
1 2  1 2
ォレフィン系ブロックポリマー（A2 )中の [S ]および [S ]と同一である。イメージ式（Π  Same as [S] and [S] in the olefin block polymer (A2). Image formula (Π
1 1 2  1 1 2
)における Qの態様、並びに [S ]、 [S ]および Q力 構成されるォレフイン系ブロック  ) Q aspects and [S], [S] and Q forces
1 2  1 2
ポリマー (A2 )の代表的製造方法は本出願人によって出願され、既に公開されてい  A representative method for producing the polymer (A2) has been filed by the present applicant and has already been published.
2  2
る特開 2004— 131620号公報に開示されている方法を制限無く使用することができ る。代表的には、ォレフィン系ブロックポリマー (A2 )は下記一般式 [C—1]で表され  The method disclosed in JP 2004-131620 A can be used without limitation. Typically, olefin block polymer (A2) is represented by the following general formula [C-1].
2  2
る構成単位と、下記一般式 [C 2]で表される構成単位および下記一般式 [C 3] で表される構成単位カゝら選ばれる少なくとも一種類の構成単位とを含む。  A structural unit represented by the following general formula [C 2] and at least one structural unit selected from the structural unit represented by the following general formula [C 3].
[0206] [化 14] [0206] [Chemical 14]
—— CH2一 CH ~ —
Figure imgf000057_0001
- CH 2 one CH ~ -
Figure imgf000057_0001
[ C- 1 ] [ C- 2 ] [ C- 3 ]  [C- 1] [C- 2] [C- 3]
[0207] 一般式 [C—1]における R1は、水素原子または炭素原子数 1〜18の直鎖状もしく は分岐状の脂肪族炭化水素基を示し、一般式 [C 2]および一般式 [C 3]におけ る R2は炭素原子数 1〜18の直鎖もしくは分岐状の脂肪族もしくは芳香族の炭化水素 基を示し、一般式 [C— 3]における F1はへテロ原子またはへテロ原子を含む基を示し 、一般式 [C 2]および一般式 [C 3]における F2は不飽和基を含む基を示し、 Zは ラジカル重合によって得られる重合体セグメントを示し、 Wはアルコール性水酸基、フ ノール性水酸基、カルボン酸基、カルボン酸エステル基、酸無水物基、アミノ基、ェ ポキシ基、シロキシ基およびメルカプト基力 選ばれる基を示し、 nは 1〜3の整数、 m は 0、 1または 2であり、 nが 2または 3のとき Zは互いに同一でも異なっていてもよぐ m 力 のとき Wは互いに同一でも異なっていてもよぐ Wは R1の同一または異なる原子 に環状構造で結合して 、ても良 、。 [0207] R 1 in the general formula [C-1] represents a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the general formula [C 2] and the general formula R 2 in the formula [C 3] represents a linear or branched aliphatic or aromatic hydrocarbon group having 1 to 18 carbon atoms, and F 1 in the general formula [C-3] is a heteroatom. Or a group containing a hetero atom, F 2 in the general formulas [C 2] and [C 3] represents a group containing an unsaturated group, Z represents a polymer segment obtained by radical polymerization, and W Represents an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxylic acid group, a carboxylic acid ester group, an acid anhydride group, an amino group, an epoxy group, a siloxy group, and a mercapto group, and n is an integer of 1 to 3 , M is 0, 1 or 2, and when n is 2 or 3, Z may be the same or different m W can be the same or different from each other W is the same or different atom in R 1 It may be bonded with a ring structure.
[0208] なお、ォレフィン系ブロックポリマー（A2 )が、前記 [C— 2]のみ力も構成されている  [0208] The olefin-based block polymer (A2) is composed of only the force [C-2].
2  2
仮想的なケースでは、骨格 [C— 2]中の主鎖部分（一 CH—CH—）が前記で表され  In the hypothetical case, the main chain part (one CH—CH—) in the skeleton [C-2] is represented above.
2  2
るイメージ式 (ii)における [S ]に相当し、骨格 [C 2]中の Zが前記イメージ式 (ii)に  Is equivalent to [S] in the image equation (ii), and Z in the skeleton [C 2] is the image equation (ii).
1  1
おける [S ]に相当し、その他残り部分（一 R2 (W )—F2 ）が前記イメージ式の Qに Is equivalent to [S], and the other remaining part (one R 2 (W) —F 2 )
2 m  2 m
相当する。  Equivalent to.
[0209] ォレフィン系ブロックポリマー（A2 )における、ポリオレフインセグメント [S ]の数平  [0209] The number of polyolefin segments [S] in the olefin block polymer (A2)
2 1 均分子量および極性ポリマーセグメント [S ]の数平均分子量は、ォレフィン系ブロッ  2 1 Average molecular weight and number average molecular weight of polar polymer segment [S]
2  2
クポリマー（A2 )と同じく各々、 1，000〜1，000，000の範囲、および 1，000〜500，0  As in the case of the copolymer (A2), the range is 1,000 to 1,000,000 and 1,000 to 500,0 respectively.
1  1
00の範囲である。  The range is 00.
[0210] また、ォレフィン系ブロックポリマー（A2 )における平均側鎖数が、ブロック（b)がブ  [0210] The average number of side chains in the olefin block polymer (A2) is
2  2
ロック（a)—分子鎖当たり通常 0. 5〜5個、好ましくは 0. 5〜3個、より好ましくは 0. 7 〜2個であると、流動性と接着性能に優れた榭脂組成物が提供される。  Lock (a) —A resin composition having excellent fluidity and adhesive performance when it is usually 0.5 to 5, preferably 0.5 to 3, more preferably 0.7 to 2 per molecular chain Is provided.
[0211] 以上、ォレフィン系ブロックポリマー（A2 )および (A2 )について詳説した。 [0211] The olefin-based block polymers (A2) and (A2) have been described in detail above.
1 2  1 2
[0212] 前記ォレフィン系ブロックポリマー（A2)、好ましくはォレフイン系ブロックポリマー（A 2 )および Zまたはォレフィン系ブロックポリマー (A2 )を層 (L2)に用いる場合には、 [0212] When the olefin-based block polymer (A2), preferably the olefin-based block polymer (A 2) and Z or olefin-based block polymer (A2) are used in the layer (L2),
1 2 1 2
ォレフィン系ブロックポリマー（A2)における極性ポリマーセグメント [S ]の割合、 [S ]  Ratio of polar polymer segment [S] in olefin block polymer (A2), [S]
2 2 twenty two
/ ( [S ] + [S ]) (重量0 /0)は、 1%〜60%が好ましぐ 2〜30%がより好ましぐ 3〜1/ ([S] + [S ]) ( weight 0/0) is from 1% to 60% is preferred instrument 2-30% and more preferably fixture 3-1
1 2 1 2
5%が特に好ましい。極性ポリマーセグメント [S2]の割合がこの範囲にあると、層（L2 )の中でォレフィン系ブロックポリマー（A2)へ溶解性が高まり、層（L3)への溶解性. 反応性が高いために層 (L2)と層 (L3)との接着強度が高まる。  5% is particularly preferred. If the ratio of the polar polymer segment [S2] is within this range, the solubility in the olefin-based block polymer (A2) in the layer (L2) is increased and the solubility in the layer (L3) is high. Adhesive strength between layer (L2) and layer (L3) is increased.
[0213] 本発明の積層構造体を構成する層（L2)は、前記ォレフィン系ブロックポリマー (A2 )、好ましくはォレフイン系ブロックポリマー（A2 )および [0213] The layer (L2) constituting the laminated structure of the present invention comprises the olefin-based block polymer (A2), preferably the olefin-based block polymer (A2) and
1 Zまたはォレフィン系ブロック ポリマー（A2 )を含んでなる層である。通常は、ォレフィン系ブロックポリマー（A2)を  1 A layer comprising Z or olefin-based block polymer (A2). Usually, olefin block polymer (A2)
2  2
必須構成成分として、前記ポリオレフインセグメント [S ]と同質のポリオレフイン [R]お  As an essential component, the polyolefin segment [S] is the same as the polyolefin segment [S].
1  1
よび、前記した極性ポリマーセグメント [S ]と同質の極性ポリマー [Q]から選ばれる 1  And a polar polymer [Q] of the same quality as the polar polymer segment [S] described above 1
2  2
種以上から構成される。なお、本発明において「同質の」とは、ポリオレフインセグメン ト [S ]中の、極性ポリマーセグメント [S ]と結合している炭素原子、或いは極性ポリマ 一セグメント [s ]中の、ポリオレフインセグメント [s ]と結合している炭素原子が水素 Consists of more than species. In the present invention, “homogeneous” means a carbon atom or polar polymer bonded to the polar polymer segment [S] in the polyolefin segment [S]. In one segment [s], the carbon atom bonded to the polyolefin segment [s] is hydrogen.
2 1  twenty one
原子で置換された化学構造を持つ、各々ポリオレフイン或 、は極性ポリマーとして定 義される。し力しながら本発明においては、前記ポリオレフイン [R]としては、極性ポリ マーセグメント [S ]と結合して!/ヽる炭素原子が水素原子で置換された化学構造のポ  Each of the polyolefins or chemicals having a chemical structure substituted with atoms is defined as a polar polymer. However, in the present invention, the polyolefin [R] has a chemical structure in which the carbon atom bonded to the polar polymer segment [S] is replaced with a hydrogen atom.
2  2
リオレフインのみならず、分子量が変動したものや α—ォレフィン導入率が異なるポリ ォレフィンも [R]の対象であり、前記した層（L1)を構成ずるォレフイン系重合体として 例示したォレフィン系重合体を制限なく使用できるのである。一方で極性ポリマー [Q ]としては、ポリオレフインセグメント [S ]と結合している炭素原子が水素原子で置換さ  Polyolefins with different molecular weights and different α-olefin introduction rates are also subject to [R] as well as rioolefin, and the olefin polymers exemplified as the olefin polymers constituting the layer (L1) described above are also subject to [R]. It can be used without restriction. On the other hand, in the polar polymer [Q], the carbon atom bonded to the polyolefin segment [S] is replaced with a hydrogen atom.
1  1
れたィ匕学構造の極性ポリオレフインのみならず、分子量が変動したもの、極性モノマ 一の導入率が異なるものも全て [Q]の対象となる。  In addition to polar polyolefins with a well-structured structure, those with varying molecular weights and those with different rates of introduction of polar monomers are all subject to [Q].
[0214] 層（L2)における (Α2)と [Q]と [R]の合計に占めるォレフィン系ブロックポリマー (Α[0214] Olefin-based block polymer (Α) in the total of (Α2), [Q] and [R] in layer (L2)
2)の重量割合は、通常 1〜： LOO重量％、好ましくは 1〜50重量％であり、より好ましく は 1〜30重量％である。 The weight ratio of 2) is usually 1 to: LOO wt%, preferably 1 to 50 wt%, more preferably 1 to 30 wt%.
[0215] なお、層（L2)がォレフイン系ブロックポリマー (Α2)と前記極性ポリマー [Q]を含み[0215] The layer (L2) contains an olefin block polymer (Α2) and the polar polymer [Q].
、前記ポリオレフイン [R]を含まない場合は、 [Q]/[S If the polyolefin [R] is not included, [Q] / [S
2 ] (重量比）、すなわち、成分 [ 2] (weight ratio), ie the component [
Q]重量を成分 (A2)中の極性ポリマーセグメント [S ]重量で除した値力 0. 5未満、 Q] Value divided by weight of polar polymer segment [S] in component (A2) Less than 0.5,
2  2
好ましくは 0. 4未満、さらに好ましくは 0. 3未満である要件を満たすことによって、層（ L2)および層 (L3)と強力な接着力を発現する。  By satisfying the requirement of preferably less than 0.4, and more preferably less than 0.3, strong adhesive strength is developed with the layer (L2) and the layer (L3).
[0216] また、本発明に係わる層（L2)は、（A2)と [Q]と [R]以外の構成成分の共存を何ら 排除するものではない。本発明の目的を阻害しない範囲で (A2)と [Q]と [R]以外の 榭脂ゃ添加剤を添加してもよ 、。層（L2)を構成する榭脂組成物にお 、て、 (A2)と [ Q]と [R]以外の構成成分として榭脂類を添加する場合には、 (A2)と [Q]と [R]の合 計が層（L2)の 1〜： LOO重量％であり、好ましくは 50〜： LOO重量％であり、さらに好ま しくは 70〜： LOO重量％となるように添加される。また、層（L2)に添加される添加剤成 分としては、タルク、シリカ、マイ力、クレー、グラスファイバー等の無機フィラー、染顔 料、酸化防止剤、加工安定剤、耐候剤、熱安定剤、光安定剤、核剤、滑剤、離型剤 、難燃剤、帯電防止剤、着色剤、紫外線吸収剤等である。  [0216] Further, the layer (L2) according to the present invention does not exclude any coexistence of components other than (A2), [Q] and [R]. A resin additive other than (A2), [Q] and [R] may be added as long as the object of the present invention is not impaired. In the case of adding a greave as a constituent other than (A2), [Q] and [R] to the greave composition constituting the layer (L2), (A2) and [Q] The total amount of [R] is 1 to: LOO wt% of the layer (L2), preferably 50 to: LOO wt%, and more preferably 70 to: LOO wt%. Additive components added to the layer (L2) include talc, silica, My strength, clay, glass fiber, and other inorganic fillers, dyes, antioxidants, processing stabilizers, weathering agents, and heat stabilizers. Agents, light stabilizers, nucleating agents, lubricants, mold release agents, flame retardants, antistatic agents, coloring agents, ultraviolet absorbers and the like.
[0217] 層 (L2)を構成する榭脂組成物の製造方法は、従来公知の方法を採用できる。たと えば、各成分を一括で、または逐次に、ヘンシェルミキサー、 V ブレンダー、リボン ブレンダー、タンブラーブレンダ一等で混合する方法、あるいはこのような方法で混 合して得られた混合物を、さらに一軸押出機、二軸押出機、ニーダー、バンバリーミ キサ一等で溶融混練した後、造粒ある ヽは得られた榭脂塊を粉砕することによって 得ることができる。 [0217] A conventionally known method can be adopted as a method for producing the resin composition constituting the layer (L2). And For example, a method in which each component is mixed in a batch or sequentially with a Henschel mixer, V blender, ribbon blender, tumbler blender, etc., or a mixture obtained by such a method is further mixed with a single screw extruder. After melt-kneading with a twin-screw extruder, kneader, Banbury mixer, etc., a granulated soot can be obtained by pulverizing the obtained lumps.
[0218] 層（L3)  [0218] Layer (L3)
層（L3)は、極性ビニル系プラスチック、芳香族ビニル系重合体、ポリエステル、ポリ アミド、ポリカーボネート、エンジニアリングプラスチック、生物由来ポリマー、熱可塑 性エラストマ一、天然製または人工繊維、および金属から選ばれる少なくても 1種から 選ばれる層である。本発明においては、層（L3)力 極性ビュル系プラスチック又は 芳香族ビュル系重合体から構成されておる場合において、層（L2)との層間で優れ た接着性能を示す。  The layer (L3) is at least selected from polar vinyl plastics, aromatic vinyl polymers, polyesters, polyamides, polycarbonates, engineering plastics, biological polymers, thermoplastic elastomers, natural or artificial fibers, and metals. But it is a layer selected from one kind. In the present invention, in the case where the layer (L3) is composed of a polar bull-type plastic or an aromatic bull-type polymer, excellent adhesion performance between the layer (L2) and the layer (L2) is exhibited.
[0219] 層（L3)において用いられる極性ビュル系プラスチックとして具体的には、アクリル 系重合体、塩化ビニル系重合体、塩化ビニリデン系重合体、エチレン 酢酸ビニル 共重合体酸ィ匕物などを例示することができる。  [0219] Specific examples of the polar bull plastic used in the layer (L3) include acrylic polymers, vinyl chloride polymers, vinylidene chloride polymers, ethylene vinyl acetate copolymer oxides, and the like. can do.
[0220] 層（L3)にお 、て用いられる芳香族ビュル重合体とは、芳香族ビュル単量体を成分 として含有する単量体を重合して得られる重合体のことである。芳香族ビニル単量体 の例としては、スチレン、 a—メチノレスチレン、 p—メチルスチレンを挙げることができ る。芳香族ビニル重合体の例としては、芳香族ビュル単独重合体のみならず、ブタジ ェンゴム、スチレン ブタジエン共重合体、エチレン プロピレン共重合体、エチレン プロピレン ジェン共重合体等の各種ゴム質重合体を含有する芳香族ビニル重 合体、スチレン 無水マレイン酸共重合体、スチレンーメタクリル酸メチル共重合体、 スチレン—アクリロニトリル共重合体、スチレン—アクリロニトリル ブタジエン共重合 体、スチレン—アクリロニトリル アクリル酸エステル共重合体等を例示することができ る。  [0220] The aromatic bull polymer used in the layer (L3) is a polymer obtained by polymerizing a monomer containing an aromatic bull monomer as a component. Examples of aromatic vinyl monomers include styrene, a-methylol styrene, and p-methyl styrene. Examples of aromatic vinyl polymers include not only aromatic butyl homopolymers, but also various rubber polymers such as butadiene rubber, styrene butadiene copolymer, ethylene propylene copolymer, and ethylene propylene copolymer. Aromatic vinyl polymer, styrene maleic anhydride copolymer, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile butadiene copolymer, styrene-acrylonitrile acrylate copolymer, etc. It can be illustrated.
[0221] 層（L3)において用いられるポリエステルとしては、ポリマー主鎖にエステル結合を 有し、加熱溶融が可能なものであれば特に制限されない。本発明で用い得るポリェ ステルとしては、例えば、ジカルボン酸成分とジオール成分との反応により得られるポ リエステル、ラタトンを開環重合して得られるポリエステル (ポリラタトン）、ヒドロキシカ ルボン酸またはそのエステル形成誘導体を重縮合して得られるポリエステルなどを挙 げることができ、これらのポリエステルの一種または二種以上を用いることができる。そ のうちでも、本発明では、ジカルボン酸成分とジオール成分とから実質的に形成され て ヽるポリエステルが好ましく用いられる。ポリエステルの原料である上記したジカル ボン酸成分の具体例としては、テレフタル酸、フタル酸、イソフタル酸、ナフタレンジ力 ルボン酸、ビス（p—カルボキシフエ-ル）メタン、アントラセンジカルボン酸、 4,4'ージ フエ-ルエーテルジカルボン酸、 5—スルホイソフタル酸ナトリウムなどの芳香族ジカ ルボン酸；グルタル酸、アジピン酸、ピメリン酸、スベリン酸、セバシン酸、ァゼライン酸 、ドデカンジオン酸などの脂肪族ジカルボン酸；シクロへキサンジカルボン酸などの脂 環式ジカルボン酸;マレイン酸、フマル酸、ィタコン酸などの不飽和脂肪族ジカルボ ン酸；テトラブロモフタル酸などのハロゲン含有ジカルボン酸；およびそれらのエステ ル形成性誘導体などを挙げることができる。 [0221] The polyester used in the layer (L3) is not particularly limited as long as it has an ester bond in the polymer main chain and can be melted by heating. Examples of the polyester that can be used in the present invention include a polyester obtained by a reaction of a dicarboxylic acid component and a diol component. Examples include polyesters obtained by ring-opening polymerization of reesters and latatones (polylatatanes), polyesters obtained by polycondensation of hydroxycarboxylic acid or its ester-forming derivatives, and one or two of these polyesters. The above can be used. Among them, in the present invention, a polyester that is substantially formed from a dicarboxylic acid component and a diol component is preferably used. Specific examples of the above-mentioned dicarboxylic acid component that is a raw material for polyester include terephthalic acid, phthalic acid, isophthalic acid, naphthalene dicarboxylic acid rubonic acid, bis (p-carboxyphenol) methane, anthracene dicarboxylic acid, 4,4 '-Diphenyl ether dicarboxylic acid, aromatic dicarboxylic acid such as sodium 5-sulfoisophthalate; aliphatic dicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, dodecanedioic acid Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; halogen-containing dicarboxylic acids such as tetrabromophthalic acid; and their ester-forming properties Derivatives and the like can be mentioned.
[0222] また、ポリエステルの原料である上記したジオール成分の具体例としては、エチレン グリコール、プロピレングリコール、 1,4 ブタンジオール、 1,5 ペンタンジオール、 ネオペンチルグリコール、 1,6 へキサンジオール、 1,7 ヘプタンジオール、 1,8— オクタンジオール、 1,9ーノナンジオール、 1,10 デカンジオール、 3—メチルー 1,5 ペンタンジオール、 2—メチルー 1,8 オクタンジオールなどの脂肪族ジオール；シ クロへキサンジメタノール、シクロへキサンジオールなどの脂環式ジオール；ジェチレ ングリコール、ポリエチレングリコール、ポリ i,3 プロピレングリコール、ポリテトラメ チレングリコールなどの分子量 6,000以下のポリアルキレングリコールなどから誘導さ れるジオールなどを挙げることができる。 [0222] Specific examples of the above-mentioned diol component that is a raw material for polyester include ethylene glycol, propylene glycol, 1,4 butanediol, 1,5 pentanediol, neopentyl glycol, 1,6 hexanediol, 1 , 7 Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 decanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8 octanediol and other aliphatic diols; Examples include cycloaliphatic diols such as sandimethanol and cyclohexanediol; diols derived from polyalkylene glycols with a molecular weight of 6,000 or less, such as polyethylene glycol, polyethylene glycol, poly i, 3 propylene glycol, and polytetramethylene glycol. Can do.
[0223] また、ポリエステルは、必要に応じて、例えば、グリセリン、トリメチロールプロパン、 ペンタエリスリトール、トリメリット酸、ピロメリット酸などの三官能以上の化合物から誘導 される構造単位の 1種または 2種以上を少量であれば有して 、てもよ 、。  [0223] Further, the polyester may be one or two structural units derived from a trifunctional or higher functional compound such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, or pyromellitic acid, if necessary. If you have a small amount, you can have it.
[0224] 層（L3)において用いられるポリカーボネートとしては、実質的ジヒドロキシィ匕合物と 、ホスゲン、炭酸ジエステルまたはハロゲンホルメートとを反応させて得られるポリカー ボネートを挙げることができる。その場合に、原料であるジヒドロキシ化合物としては、 例えば、 2,2 ビス（4ーヒドロキシフエ-ル）プロパン（以下「ビスフエノール A」と呼ぶ 場合がある）、テトラメチルビスフエノール A、テトラブロモビスフエノール A、ビス（4— ヒドロキシフエ-ル） p ジイソプロピルベンゼン、ハイドロキノン、レゾルシノール、 4 ,4'ージヒドロキシフエ-ルなどの芳香族ジヒドロキシ化合物を挙げることができ、これ らのうちでもビスフエノール Aが好ましい。また、ポリカーボネートは、必要に応じて、 三官能以上のポリヒドロキシィ匕合物に誘導される構造単位の 1種または 2種以上を少 量であれば有して!/、てもよ！/、。 [0224] Examples of the polycarbonate used in the layer (L3) include polycarbonate obtained by reacting a substantial dihydroxy compound with phosgene, a carbonic acid diester, or a halogen formate. In that case, as a dihydroxy compound as a raw material, For example, 2,2 bis (4-hydroxyphenol) propane (hereinafter sometimes referred to as “bisphenol A”), tetramethylbisphenol A, tetrabromobisphenol A, bis (4-hydroxyphenol) p diisopropyl Aromatic dihydroxy compounds such as benzene, hydroquinone, resorcinol and 4,4'-dihydroxyphenol can be mentioned, and among these, bisphenol A is preferred. In addition, if necessary, the polycarbonate may have one or more structural units derived from trihydroxy or higher polyhydroxy compounds in small amounts! /! /.
[0225] 層（L3)において用いられるポリアミドとしては、ポリマー主鎖にアミド結合を有し、加 熱溶融が可能なものであれば特に制限されない。本発明で用い得るポリアミドとして は、例えば、三員環以上のラタタムを開環重合して得られるポリアミド (ポリラタタム）、 ω アミノ酸の重縮合により得られるポリアミド、二塩基酸とジァミンとの重縮合により 得られるポリアミドなどを挙げることができ、これらのポリアミドの 1種または 2種以上を 用!/、ることができる。 [0225] The polyamide used in the layer (L3) is not particularly limited as long as it has an amide bond in the polymer main chain and can be heated and melted. Polyamides that can be used in the present invention include, for example, polyamides obtained by ring-opening polymerization of three-membered or more ratatams (polylatatams), polyamides obtained by polycondensation of ω amino acids, and polycondensation of dibasic acids and diamines. The resulting polyamide can be used, and one or more of these polyamides can be used!
[0226] ポリアミドの原料である上記したラタタムの具体例としては、 ε一力プロラタタム、ェ ナトラクタム、力プリルラタタム、ラウリルラタタム、 a—ピロリドンなどを挙げることができ る。また、ポリアミドの原料である上記した ω アミノ酸の具体例としては、 6—ァミノ力 プロン酸、 7 ァミノヘプタン酸、 9 アミノノナン酸、 11—アミノウンデカン酸などを挙 げることができる。上記二塩基酸の具体例としては、マロン酸、ジメチルマロン酸、コ ハク酸、 3,3 ジェチルコハク酸、グルタル酸、 2, 2 ジメチルダルタル酸、アジピン 酸、セバシン酸、スベリン酸などの脂肪族ジカルボン酸； 1 ,3 シクロペンタンジカル ボン酸、 1 ,4 シクロへキサンジカルボン酸などの脂環式ジカルボン酸；テレフタル酸 、イソフタル酸、 2,6 ナフタレンジカルボン酸、 2,7 ナフタレンジカルボン酸、 1 ,4 —ナフタレンジカルボン酸、 1 ,4 フエ-レンジォキシジ酢酸、 1 ,3 フエ-レンジォ キシジ酢酸、ジフェン酸、 4,4'ーォキシジ安息香酸、ジフエ-ルメタン—4,4'ージカル ボン酸、ジフエ-ルスルホン— 4,4'ージカルボン酸、 4,4'ージフエ-ルジカルボン酸 などの芳香族ジカルボン酸などを挙げることができる。また、上記ジァミンの具体例と しては、エチレンジァミン、プロピレンジァミン、 1 ,4 ブタンジァミン、 1 ,6 へキサン ジァミン、 1 ,8 オクタンジァミン、 1 ,9ーノナンジァミン、 1 , 10—デカンジァミン、 1 , 12 ードデカンジァミン、 2—メチルー 1,5 ペンタンジァミン、 3—メチルー 1,5 ペンタン ジァミンなどの脂肪族ジァミン；シクロへキサンジァミン、メチルシクロへキサンジァミン 、イソホロンジァミンなどの脂環式ジァミン； p—フエ-レンジァミン、 m—フエ-レンジ ァミン、キシリレンジァミン、キシレンジァミン、 4,4'ージアミノジフエ二ノレメタン、 4,4' ジアミノジフエ-ルスルホン、 4,4'ージアミノジフエ-ルエーテルなどの芳香族ジァミン を挙げることができる。 [0226] Specific examples of the above-described ratatam, which is a raw material for polyamide, include epsilon prolactam, enatoractam, force prilllatatam, lauryllatatam, a-pyrrolidone and the like. Further, specific examples of the above-mentioned ω-amino acid that is a raw material of polyamide include 6-amino force proic acid, 7 aminoheptanoic acid, 9 aminononanoic acid, 11-aminoundecanoic acid and the like. Specific examples of the dibasic acid include aliphatic acids such as malonic acid, dimethylmalonic acid, succinic acid, 3,3 jetylsuccinic acid, glutaric acid, 2,2 dimethyldaltaric acid, adipic acid, sebacic acid, and suberic acid. 1,3 cyclopentanedicarboxylic acid, 1,4 cycloaliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, 2,6 naphthalenedicarboxylic acid, 2,7 naphthalenedicarboxylic acid, 1, 4 —Naphthalenedicarboxylic acid, 1,4 phenoldioxydiacetic acid, 1,3 phenoldioxydiacetic acid, diphenic acid, 4,4′-oxydibenzoic acid, diphenylmethane—4,4′-dicarboxylic acid, diphenylsulfone— Aromatic dicarboxylic acids such as 4,4′-dicarboxylic acid and 4,4′-diphenyldicarboxylic acid can be used. Specific examples of the above diamine include ethylene diamine, propylene diamine, 1,4 butane diamine, 1,6 hexane diamine, 1,8 octane diamine, 1,9-nonane diamine, 1,10-decandiamine, 1,12 Aliphatic diamines such as dodecane diamine, 2-methyl-1,5-pentane diamine, 3-methyl-1,5-pentane diamine; cycloaliphatic diamines such as cyclohexane diamine, methyl cyclohexane diamine, and isophorone diamine; p-phenol -Aromatic diamines such as -rangeamine, m-phenol-diamine, xylylenediamine, xylenediamine, 4,4'-diaminodiphenolinolemethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether .
[0227] 層（L3)にお 、て用いられるアクリル系重合体としては、（メタ）アクリル酸エステルか ら誘導される構造単位から主としてなるアクリル系重合体を挙げることができる。その 場合に、アクリル系重合体における (メタ)アクリル酸エステル力 誘導される構造単 位の割合が 50重量％以上であることが好ましぐ 80重量％以上であることがより好ま しい。アクリル系重合体を構成する (メタ)アクリル酸エステルとしては、例えば、（メタ） アクリル酸メチル、 （メタ）アクリル酸ェチル、 （メタ）アクリル酸プロピル、 （メタ）アクリル 酸ブチル、 （メタ）アクリル酸 2—ェチルへキシルなどの（メタ）アクリル酸のアルキルェ ステルを挙げることができ、アクリル系重合体はこれらの（メタ）アクリル酸エステルの 1 種または 2種以上力 誘導される構造単位を有していることができる。また、アクリル 系重合体は、必要に応じて、（メタ)アクリル酸エステル以外の不飽和単量体力 誘導 される構造単位の 1種または 2種以上を有していてもよい。例えば、メタクリル系榭脂 は、（メタ)アクリロニトリルなどのシアンィ匕ビュル系単量体力 誘導される構造単位を 好ましくは 50重量％以下の割合で有していてもよぐまたスチレン、 o—メチルスチレ ン、 m—メチノレスチレン、 p—メチノレスチレン、 o クロロスチレン、 m—クロロスチレン、 p クロロスチレンなどの芳香族ビ-ルイ匕合物力 誘導される構造単位などを好ましく は 10重量％以下の割合で有して 、てもよ 、。  [0227] Examples of the acrylic polymer used in the layer (L3) include an acrylic polymer mainly composed of a structural unit derived from a (meth) acrylic acid ester. In that case, the proportion of structural units induced by (meth) acrylic acid ester force in the acrylic polymer is preferably 50% by weight or more, more preferably 80% by weight or more. Examples of the (meth) acrylic acid ester constituting the acrylic polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Examples include alkyl esters of (meth) acrylic acid such as 2-ethylhexyl acid, and acrylic polymers have one or more of these (meth) acrylic acid ester-derived structural units. Can be. In addition, the acrylic polymer may have one or more structural units derived from the unsaturated monomer force other than the (meth) acrylic acid ester, if necessary. For example, methacrylic resin may have a structural unit derived from a cyanobyl monomer such as (meth) acrylonitrile, preferably in a proportion of 50% by weight or less, and styrene, o-methylstyrene. , M-methylol styrene, p-methylol styrene, o chlorostyrene, m-chlorostyrene, p chlorostyrene, etc. Have it with, ok.
[0228] 層（L3)にお 、て用いられる塩ィ匕ビュル系重合体としては、塩化ビニル単独重合体 、塩ィ匕ビュルに由来する構造単位を 70重量％以上の割合で有する塩ィ匕ビ二ルと他 の共重合性単量体との共重合体およびそれらの塩素化物の 1種または 2種以上が好 ましく用いられる。塩ィ匕ビュル系重合体が塩ィ匕ビニル共重合体である場合は、塩ィ匕ビ -ルと、エチレン、プロピレン、酢酸ビュル、臭化ビュル、塩化ビ-リデン、アタリ口-ト リル、マレイミドなどの共重合性単量体の 1種または 2種以上の共重合体が好ましく用 いられる。塩ィ匕ビニル系重合体の重合度は特に制限されないが、一般に、重合度が[0228] As the salt-based polymer used in the layer (L3), a vinyl chloride homopolymer, a salted polymer having a structural unit derived from salted-bulu in a proportion of 70% by weight or more. One or more of copolymers of vinyl and other copolymerizable monomers and chlorinated products thereof are preferably used. In the case where the salt vinyl polymer is a salt vinyl copolymer, the salt vinyl, ethylene, propylene, butyl acetate, butyl bromide, vinylidene chloride, tali-tril, One or more copolymers of copolymerizable monomers such as maleimide are preferably used I can. The degree of polymerization of the salt vinyl polymer is not particularly limited, but in general, the degree of polymerization is
100〜10,000のものが好ましく用いられ、 500〜6,000のものカょり好ましく用ぃら れる。 Those of 100 to 10,000 are preferably used, and those of 500 to 6,000 are preferably used.
[0229] 重合体層 (L3)において用いられる塩ィ匕ビユリデン系重合体としては、塩ィ匕ビ -リデ ンに由来する構造単位を 50重量％以上の割合で有している熱可塑性重合体が好ま しく用いられ、 70重量％以上の割合で有して 、る熱可塑性重合体がより好ましく用 、 られる。塩ィヒビ二リデン系重合体が塩ィヒビ二リデンと他の単量体との共重合体である 場合には、塩ィ匕ビユリデンと、塩化ビュル、アクリロニトリル、アクリル酸エステルおよ びアクリル酸などの他の不飽和単量体の 1種または 2種以上との共重合体が好ましく 用いられる。塩ィ匕ビ二リデン系重合体の重合度は特に制限されないが、一般に、重 合度が 100〜10,000のものが好ましく用いられ、 500〜5,000のもの力 り好ましく 用いられる。  [0229] The salt vinylidene polymer used in the polymer layer (L3) is a thermoplastic polymer having a structural unit derived from salt vinylidene in a proportion of 50% by weight or more. Is preferably used, and the thermoplastic polymer having a ratio of 70% by weight or more is more preferably used. When the salt vinylidene-based polymer is a copolymer of salt vinylidene and other monomers, such as salt vinylidene and butyl chloride, acrylonitrile, acrylate ester and acrylic acid. Copolymers with one or more other unsaturated monomers are preferably used. The polymerization degree of the vinyl chloride vinylidene-based polymer is not particularly limited, but in general, those having a polymerization degree of 100 to 10,000 are preferably used, and those having a polymerization degree of 500 to 5,000 are preferably used.
[0230] 層（L3)において用いられるエチレン 酢酸ビュル共重合体酸ィ匕物としては、ェチ レン含量が 20〜60モル0 /0、好ましくは 25〜60モル％で、ケン化度が 95%以上のも のが好ましく用いられる。また、エチレン 酢酸ビュル共重合体ケンィ匕物は、 ASTM D— 1238— 65Tに準拠して測定したメルトインデックスが 0. l〜25gZlO分（190 。C、 2. 16kg荷重下で測定)であること力 成形性の点から好ましぐ 0. 3〜20gZlO 分であることがより好ましい。 [0230] layer of an ethylene acetate Bulle copolymer Sani匕物used in (L3) is E Ji Ren content 20 to 60 mole 0/0, preferably 25 to 60 mol%, a degree of saponification of 95 More than% is preferably used. In addition, the ethylene acetate butyl copolymer cans have a melt index measured according to ASTM D-1238-65T of 0.1 to 25 gZlO (measured at 190 C, 2.16 kg load). It is more preferably 0.3 to 20 gZlO content from the viewpoint of moldability.
[0231] 層（L3)において用いられるエンジニアリングプラスチックの代表的例は、ポリアセタ ール（POM)、ポリフエ-レンエーテル（変性ポリフエ-レンエーテルを含む）、ポリサ ルホン（PSF)、ポリエーテルサルホン（PES)、ポリフエ-レンサルファイド、ポリアリレ 一 HUポリマー）、ポリアミドイミド、ポリエーテルケトン（PEK)、ポリエーテルエーテル ケトン（PEEK)、ポリイミド（PI)、液晶ポリエステル等のスーパーエンジニアリングプラ スチック等である。  [0231] Typical examples of engineering plastics used in the layer (L3) include polyacetal (POM), polyphenylene ether (including modified polyphenylene ether), polysulfone (PSF), polyethersulfone ( PES), polyphenylene sulfide, polyarylene HU polymer), polyamideimide, polyetherketone (PEK), polyetheretherketone (PEEK), polyimide (PI), super engineering plastics such as liquid crystal polyester.
[0232] 層（L3)において用いられる生物由来ポリマーとは、植物や動物といった生物由来 の原料である「バイオマス」からつくられる生物由来のポリマーであり、その代表的例 は、ポリ 3—ヒドロキシ酪酸（PHB)、ポリ乳酸、ポリダリコール酸、ポリ力プロラタトン 、ポリヒドロキシブチレート、またはこれらの共重合体、でんぷん、セルロース、力-や ェビの甲羅などの成分であるキチン'キトサン、ケナフ、天然ゴム等が挙げられる。 [0232] The biological polymer used in the layer (L3) is a biological polymer made from "biomass" which is a raw material of biological origin such as plants and animals. A typical example is poly-3-hydroxybutyric acid. (PHB), polylactic acid, polydaricholic acid, poly strength prolatatone, polyhydroxybutyrate, or a copolymer thereof, starch, cellulose, strength Examples include chitin, chitosan, kenaf, and natural rubber, which are ingredients such as shrimp shells.
[0233] 層（L3)において用いられる天然製または人工繊維とは、ガラス繊維、炭素繊維、 金属繊維、芳香族ポリアミド繊維、ポリアラミド繊維、アルミナ繊維、炭化珪素繊維、ボ ロン繊維、玄武岩繊維などが挙げられる。  [0233] Natural or artificial fibers used in the layer (L3) include glass fibers, carbon fibers, metal fibers, aromatic polyamide fibers, polyaramid fibers, alumina fibers, silicon carbide fibers, boron fibers, basalt fibers, and the like. Can be mentioned.
[0234] 層（L3)において用いられる金属とは、代表的にはアルミニウム、鉄、マグネシウム、 チタンおよびこれらとの合金等に、熱接着性の表面処理を施した金属材料が挙げら れる。 [0234] The metal used in the layer (L3) typically includes a metal material obtained by subjecting aluminum, iron, magnesium, titanium, an alloy thereof, or the like to a heat-adhesive surface treatment.
[0235] 穑層構； ί告体  [0235] 穑 层 构;
本発明の積層構造体では、各層の厚さは特に制限されず、各層を構成する重合体 または材料の種類、積層構造体における全体の層数、積層構造体の用途などに応 じて調節し得る力 一般には、重合体層 (L1)の厚さを 10 m〜5mm、重合体層（L In the laminated structure of the present invention, the thickness of each layer is not particularly limited and may be adjusted according to the type of polymer or material constituting each layer, the total number of layers in the laminated structure, the use of the laminated structure, and the like. Generally, the thickness of the polymer layer (L1) is 10 m to 5 mm and the polymer layer (L
2)の厚さを 1 μ m〜lmm、重合体層（L3)の厚さを 10 μ m〜5mmにしておくことが、 積層構造体の製造の容易性、層間接着力などの点力も好ましい。 The thickness of 2) should be 1 μm to lmm and the thickness of the polymer layer (L3) should be 10 μm to 5 mm. .
[0236] また、本発明の積層構造体における全体の層数は特に制限されず、層 (L1)Z層（ L2)Z層（L3)の順に積層している構造を少なくとも一部に有する積層構造体である 限りはいずれでもよい。また、本発明の積層構造体は、層（L1)、層（L2)および層 (L [0236] Further, the total number of layers in the multilayer structure of the present invention is not particularly limited. Any may be used as long as it is a structure. The laminated structure of the present invention includes a layer (L1), a layer (L2)
3)の三層のみ力も形成されていても、またはそれらの三種の層と共に、層（L1)〜層 (L3)を構成している材料以外の他の材料力もなる層の 1つまたは 2つ以上を有して いてもよい。 Even if only the three layers of 3) are formed, or together with these three layers, one or two of the layers that have other material forces other than the materials constituting the layers (L1) to (L3) You may have the above.
[0237] 本発明の積層構造体の例としては、層（LI) Z層（L2) Z層（L3)力 なる 3層構造 物;層 (L3) Z層（LI) Z層（L2) Z層（L3)力もなる 4層構造物;層（LI) Z層（L2) / 層（L3) Z層（L2) Z層（L1)力 なる 5層構造物;層 (L3) Z層（L2) Z層（LI) Z層（ L2) Z層（L3)力 なる 5層構造物;層 (L3) Z層（LI) Z層（L2) Z層（L3) Z層（L2 ) Z層 (LI) Z層 (L3)力もなる 7層構造物などを挙げることができる。  [0237] Examples of the laminated structure of the present invention include layer (LI) Z layer (L2) Z layer (L3) force three-layer structure; layer (L3) Z layer (LI) Z layer (L2) Z Layer (L3) Force 4 layer structure; Layer (LI) Z layer (L2) / Layer (L3) Z layer (L2) Z layer (L1) Force 5 layer structure; Layer (L3) Z layer (L2 ) Z layer (LI) Z layer (L2) Z layer (L3) force 5 layer structure; layer (L3) Z layer (LI) Z layer (L2) Z layer (L3) Z layer (L2) Z layer ( LI) Z layer (L3) 7 layer structure that also has force.
[0238] 本発明の積層構造体の製造法としては、例えば、  [0238] As a method for producing the laminated structure of the present invention, for example,
(1)層（L1)用の重合体、層（L2)用の重合体および層（L3)用の重合体又は材料を 少なくとも用いて、それらをフィルム状、シート状、板状に溶融共押出成形して、それ ぞれの層の押出成形と同時に積層させて積層構造体を製造する方法； (2)層（LI)を構成するフィルム、シート、板などを予め製造しておき、および Zまた は層（L3)を構成するフィルム、シート、板などの成形品を予め製造しておき、重合体 層（L2)を溶融押出成形しながら、また層（L1)および層 (L3)の一方が予め成形され たものでない場合はそれをも溶融押出成形しながら、予め製造しておいた層（L1)用 の成形品および Zまたは層（L3)用の成形品と積層して一体化させて積層構造体を 製造する方法； (1) At least the polymer for layer (L1), the polymer for layer (L2) and the polymer or material for layer (L3) are melt-coextruded into a film, sheet or plate A method of forming a laminated structure by forming and laminating simultaneously with extrusion molding of each layer; (2) A film, a sheet, a plate, etc. constituting the layer (LI) are produced in advance, and a molded product such as a film, a sheet, a plate constituting the Z or layer (L3) is produced in advance, A layer prepared in advance while melt-extrusion of the polymer layer (L2) and, if one of the layers (L1) and (L3) is not preformed, it is also melt-extruded. A method for producing a laminated structure by laminating and integrating a molded product for (L1) and a molded product for Z or layer (L3);
(3)層（L1)を構成するフィルム、シート、板などの成形品と、層（L3)を構成するフィ ルム、シート、板などの成形品を予め製造しておき、更に層（L2)用の重合体も予め フィルムやシート状に成形しておき、層（L2)用のフィルムまたはシートを層（L1)用の 成形品と層（L3)用の成形品との間に挟んで加熱下に層（L2)用のフィルムまたはシ ートを溶融させて層 (L1)と層 (L3)を層 (L2)を介して接着 '一体化させて積層構造 体を製造する方法；  (3) A molded product such as a film, a sheet or a plate constituting the layer (L1) and a molded product such as a film, a sheet or a plate constituting the layer (L3) are manufactured in advance, and the layer (L2) The polymer for use is also formed into a film or sheet in advance, and the layer (L2) film or sheet is sandwiched between the layer (L1) molded product and the layer (L3) molded product and heated. A method of producing a laminated structure by fusing a film or sheet for the layer (L2) below and bonding the layer (L1) and the layer (L3) together through the layer (L2);
(4)層（L1)用の重合体、層（L2)用の重合体および層（L3)用の重合体又は材料を 少なくとも用いて、 3種類の重合体又は材料を、射出のタイミングをずらして金型内に 射出することにより、積層成形体を製造する方法;などを挙げることができる。  (4) Using at least the polymer for layer (L1), the polymer for layer (L2) and the polymer or material for layer (L3), the timing of injection of three types of polymers or materials is shifted. And a method for producing a laminated molded body by injection into a mold.
[0239] 上記の（1)〜 (4)の方法のいずれの場合にも、溶融した層 (L2)を介して層（L1)と 層 (L3)が接着されており、接着剤層が有機溶剤を含まないので、有機溶剤による自 然環境の破壊や、作業環境の悪化、溶剤の回収などの問題や手間を生ずることなく 、目的とする積層構造体を得ることができる。そのうちでも、上記した（1)の共押出成 形による方法が、工程数が少なくてすみ、生産性が高ぐしかも層（L1)、層（L2)お よび層 (C)間の接着強度が高くて、層間剥離のない積層構造体を得ることができる ので好ましい。  [0239] In any of the above methods (1) to (4), the layer (L1) and the layer (L3) are bonded via the molten layer (L2), and the adhesive layer is organic. Since it does not contain a solvent, the desired laminated structure can be obtained without causing problems and troubles such as destruction of the natural environment by organic solvents, deterioration of the working environment, and recovery of the solvent. Among them, the above-described method (1) by coextrusion molding requires fewer steps, increases productivity, and provides adhesion strength between layers (L1), (L2) and (C). It is preferable because it is high and a laminated structure without delamination can be obtained.
[0240] 共押出成形法によって本発明の積層構造体を製造する場合は、積層構造体の層 数などに応じて、例えば 3台以上の押出機を 1つのダイに結合して、複数の重合体を ダイの内側または外側で積層一体ィ匕して製造することができる。その場合のダイとし ては、 Tダイ、環状ダイなどを使用することができ、押出機やダイの形状や構造などは 特に制限されない。  [0240] When the laminated structure of the present invention is produced by the co-extrusion molding method, for example, three or more extruders are connected to one die according to the number of layers of the laminated structure, and a plurality of weights are combined. The coalescence can be produced by stacking together on the inside or outside of the die. In this case, a T die, an annular die, or the like can be used as the die, and the shape and structure of the extruder and the die are not particularly limited.
[0241] 本発明の積層構造体は、それを構成している層 (L1)、層 (L2)、層 (L3)の性質な どに応じて種々の用途に使用することができ、例えば、食品や医療用薬剤の包装材 料；衣料用包装材料；その他の製品用の包装材料；壁紙や化粧板などのような建材 用；電気絶縁用フィルム；粘着フィルムやテープ用基材；マーキングフィルム；農業用 フィルム；テーブルクロス、レインコート、傘、カーテン、カバー類などの雑貨用；金属 板やその他の材料とのラミネート用などの種々の用途に使用することができる。 産業上の利用可能性 [0241] The laminated structure of the present invention has the properties of the layer (L1), the layer (L2), and the layer (L3) constituting the layered structure. It can be used for various purposes, such as packaging materials for food and medical drugs; packaging materials for clothing; packaging materials for other products; for building materials such as wallpaper and decorative boards; Film for electrical insulation; base material for adhesive film and tape; marking film; film for agriculture; various items such as table cloth, raincoat, umbrella, curtain, cover, etc .; for laminating with metal plates and other materials Can be used for Industrial applicability
[0242] 本発明の積層構造体は、層間の接着強度が極めて高く層間の剥離が生じ難いの で、食品や医療用薬剤の包装材料、衣料用包装材料、その他の製品用の包装材料 、壁紙やィ匕粧板などのような建材用、電気絶縁用フィルム、粘着フィルムやテープ用 基材、マーキングフィルム、農業用フィルム、テーブルクロス、レインコート、傘、カー テン、カバー類などの雑貨用、金属板やその他の材料とのラミネート用などの種々の 用途に有効に使用することができる。  [0242] The laminated structure of the present invention has extremely high interlayer adhesive strength and is unlikely to delaminate. Therefore, packaging materials for foods and medical drugs, packaging materials for clothing, packaging materials for other products, wallpaper For building materials such as decorative panels, electrical insulation films, adhesive films and tape substrates, marking films, agricultural films, tablecloths, raincoats, umbrellas, curtains, covers, etc. It can be effectively used for various purposes such as laminating with metal plates and other materials.
[実施例]  [Example]
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれら実 施例に限定されるものではない。  EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
[0243] 以下の実施例において、各物性は以下のようにして測定'評価した。実施例および 比較例において、各種の評価に用いられた試験法を以下に示した。 [0243] In the following examples, each physical property was measured and evaluated as follows. In the examples and comparative examples, the test methods used for various evaluations are shown below.
(1) MFR  (1) MFR
MFRは、 ASTM D 1238 (230。C、荷重 2. 16kg)に従って測定した。ただし、 M FR は温度 190°C、荷重 2. 16kgの条件で測定した MFRである。  MFR was measured according to ASTM D 1238 (230.C, load 2.16 kg). However, MFR is MFR measured under conditions of temperature 190 ° C and load 2.16kg.
190  190
(2)引張り試験  (2) Tensile test
引張り試験は、 ASTM D638に準拠して、厚み lmmのプレスシートから打ち抜い たダンベル型試験片を 23°C、スパン間隔 30mm、引張り速度 30mmZ分で試験し た。但し、実施例 17〜27については、引張速度： 5mmZ分で行った。  In the tensile test, in accordance with ASTM D638, a dumbbell-shaped test piece punched from a press sheet having a thickness of 1 mm was tested at 23 ° C, a span interval of 30 mm, and a pulling speed of 30 mmZ. However, in Examples 17 to 27, the tensile rate was 5 mmZ.
(3)曲げ強度  (3) Bending strength
曲げ強度は、 ASTM D790に従って、下記の条件で測定した。  The bending strength was measured according to ASTM D790 under the following conditions.
[0244] <測定条件 > [0244] <Measurement conditions>
試験片：12.7mm (幅） X 3. 2mm (厚さ） X 127mm (長さ） 曲げ速度： 5mmZ分 Test piece: 12.7mm (width) X 3.2mm (thickness) X 127mm (length) Bending speed: 5mmZ min
曲げスパン： 100mm  Bending span: 100mm
試験片の厚み： 1Z8インチ  Test piece thickness: 1Z8 inch
(4)アイゾット衝撃強度 (IZ)  (4) Izod impact strength (IZ)
アイゾット衝撃強度 (IZ)は、 ASTM D256に準拠して下記の条件で測定した。  Izod impact strength (IZ) was measured under the following conditions in accordance with ASTM D256.
[0245] <試験条件 > [0245] <Test conditions>
温度： 23°C  Temperature: 23 ° C
試験片： 12.7mm (幅） X 3. 2mm (厚さ） X 64mm (長さ）  Test piece: 12.7mm (width) X 3.2mm (thickness) X 64mm (length)
ノッチは機械加工で作成した  The notch was made by machining
(5)はく離  (5) Peel
成形体の層はく離状態は、 ASTM— 1試験片のゲート部近傍におけるセロテープ（ 登録商標）はく離試験（3回）によって評価した。  The peeled-off state of the molded body was evaluated by a cello tape (registered trademark) peeling test (three times) in the vicinity of the gate part of the ASTM-1 test piece.
[0246] 判断基準： [0246] Criteria:
〇 … はく離無し  〇… No peeling
△ … 一部はく離有り  △… Some peeling
X … 全面はく離有り  X… Full peeling
また、ポリオレフイン、ポリカーボネート榭脂、アクリル榭脂、ビュル重合体、ポリフエ 二レンオキサイド等として以下の榭脂を使用した。  Further, the following resins were used as polyolefin, polycarbonate resin, acrylic resin, bur polymer, polyphenylene oxide and the like.
ポリオレフイン  Polyolefin
ポリオレフイン (A1— 1)：  Polyolefin (A1— 1):
株式会社プライムポリマー社製 結晶性ポリプロピレン単独重合体、 MFR= 13g/ 10分、融点 = 165°C  Crystalline polypropylene homopolymer manufactured by Prime Polymer Co., Ltd., MFR = 13g / 10min, melting point = 165 ° C
ポリオレフイン (A1— 2)：  Polyolefin (A1—2):
株式会社プライムポリマー社製 結晶性ポリプロピレン単独重合体 MFR=3gZl 0分、融点 = 163°C、 mmmm= 98. 0%  Crystalline polypropylene homopolymer manufactured by Prime Polymer Co., Ltd. MFR = 3gZl 0 min, melting point = 163 ° C, mmmm = 98.0%
ポリオレフイン (A1— 3)：  Polyolefin (A1-3):
三井化学株式会社製 タフマー A4050 (商品名） エチレン · 1—ブテンランダム共 重合体、 MFR
Figure imgf000068_0001
ポリオレフイン（Al— 4)： Tuffmer A4050 (trade name) manufactured by Mitsui Chemicals, Inc. Ethylene 1-butene random copolymer, MFR
Figure imgf000068_0001
Polyolefin (Al—4):
三井化学株式会社製 タフマー A0550(商品名） エチレン ·1—ブテンランダム共 重合体、密度 860kg/m3、 MFR =1. OgZlO分 Tuffmer A0550 (trade name) made by Mitsui Chemicals, Inc. Ethylene 1-butene random copolymer, density 860kg / m 3 , MFR = 1. OgZlO min
190  190
ポリオレフイン (Al— 5)： Polyolefin (Al—5):
株式会社プライムポリマー製 ホモポリプロピレン J106G MFR=15g/10分、引 張弾性率 1500MPa、引張破壊呼ぴひずみ 100%  Homopolypropylene made by Prime Polymer Co., Ltd.J106G MFR = 15g / 10min, Tensile modulus of elasticity 1500MPa, Tensile fracture ultimate strain 100%
ポリカーボネート榭脂 Polycarbonate resin
ポリカーボネート（B1— 1)： Polycarbonate (B1-1):
帝人化成株式会社製 パンライト L1225Y (商品名） MVR=llcm3/10min(3O 0°C、荷重 1.2kg) Panlite L1225Y (trade name) manufactured by Teijin Chemicals Limited MVR = llcm 3 / 10min (3O 0 ° C, load 1.2kg)
ポリカーボネート（B1— 2)： Polycarbonate (B1-2):
帝人化成株式会社製 パンライト AD5503(商品名） MVR=54cm3ZlOmin(30 0°C、荷重 1.2kg) Teijin Kasei Co., Ltd. Panlite AD5503 (trade name) MVR = 54cm 3 ZlOmin (3 0 0 ° C, load 1.2kg)
ポリカーボネート（B1— 3)： Polycarbonate (B1-3):
帝人化成株式会社製 パンライト L1225L (商品名） MVR=18cm3/10min(3O 0°C、荷重 1.2kg) Panlite L1225L (trade name) manufactured by Teijin Chemicals Limited MVR = 18cm 3 / 10min (3O 0 ° C, load 1.2kg)
アクリル榭 H旨 Acrylic coffee
アクリル系榭脂（B2— 1): Acrylic resin (B2— 1):
住友化学株式会社製 スミペックス MHF (商品名）  Sumipex MHF (trade name) manufactured by Sumitomo Chemical Co., Ltd.
ビュル重合体 Bull polymer
ビニル重合体（B3— 1)： Vinyl polymer (B3-1):
日本エイアンドエル株式会社製 アクリロニトリル 'ブタジエン 'スチレン共重合体（商 品名）サンタック GA101、メノレトボリュームレイト（ISOl 133、 220°C、 10kg荷重） =2 6、曲げ弾性率（IS0178、 23°C)=2600MPa  Acrylonitrile 'butadiene' styrene copolymer (trade name) SANAC GA101, Menoleto Volume Rate (ISOl 133, 220 ° C, 10kg load) = 2 6, Flexural modulus (IS0178, 23 ° C) = 2600MPa
ビニル重合体（B3— 2)： Vinyl polymer (B3-2):
日本エイアンドエル株式会社製 アクリロニトリル 'ブタジエン 'スチレン共重合体（商 品名）サンタック SXD220、メルトボリュームレイト（IS01133、 220。C、 10kg荷重） = 90、曲げ弾性率（IS0178、 23°C)=2650MPa ビニル重合体（B3— 3)： Acrylonitrile 'butadiene' styrene copolymer (trade name) Santac SXD220, melt volume rate (IS01133, 220. C, 10kg load) = 90, flexural modulus (IS0178, 23 ° C) = 2650MPa Vinyl polymer (B3-3):
日本ポリスチレン株式会社製 汎用ポリスチレン （商品名）日本ポリスチ G430 ビニル重合体（B3— 4)：  General polystyrene manufactured by Nippon Polystyrene Co., Ltd. (trade name) Nippon Polystyrene G430 Vinyl polymer (B3-4):
日本エイアンドエル株式会社製 アクリロニトリル 'スチレン共重合体 (商品名）ライタ ック 100PCF、メル卜ボリュームレイ卜（ISOl 133、 220。C、 10kg荷重） = 18、曲げ弹 性率（IS0178、 23。 = 3600MPa  Acrylonitrile styrene copolymer (trade name) manufactured by Nippon A & L Co., Ltd. (trade name) 100PCF, Mel volume volume (ISOl 133, 220. C, 10kg load) = 18, Bending modulus (IS0178, 23. = 3600MPa
ポリフエ二レンオキサイド Polyphenylene oxide
ポリフエ-レンオキサイド（B4—1)： Polyphenolene oxide (B4-1):
日本ジーィ一プラスチックス株式会社製 ノリル 115 (商品名）  Noryl 115 (trade name) manufactured by Nippon Gichi Plastics Co., Ltd.
ポリフエ-レンオキサイド（B4— 2)： Polyphenylene oxide (B4-2):
日本ジーィ一プラスチックス株式会社製 ノリル 646 (商品名）  Nilil 646 (trade name) manufactured by Nippon Gichi Plastics Co., Ltd.
その他,の 旨 Others
A3400 : A3400:
日本油脂株式会社製 モディパー A3400 (商品名） ポリプロピレン—ポリ (スチレ ン ·アクリロニトリル共重合体)ブロックポリマー  MODIPER A3400 (trade name) Polypropylene-Poly (styrene / acrylonitrile copolymer) block polymer
A3100 : A3100:
日本油脂株式会社製 モディパー A3100 (商品名） ポリプロピレン—ポリスチレン ブロックポリマー  MODIPER A3100 (trade name) made by Nippon Oil & Fat Co., Ltd. Polypropylene—Polystyrene Block polymer
H1041 : H1041:
旭化成ケミカルズ株式会社製 タフテック H1041 (商品名） ポリスチレン ポリ（ェ チレン'ブテン） ポリスチレンブロック共重合体  Asahi Kasei Chemicals Corporation Tuftec H1041 (trade name) Polystyrene Poly (Ethylene 'Butene) Polystyrene Block Copolymer
H1043 : H1043:
旭化成ケミカルズ株式会社製 タフテック H1043 (商品名） ポリスチレン—ポリ（ェ チレン'ブテン） ポリスチレンブロック共重合体  Asahi Kasei Chemicals Co., Ltd. Tuftec H1043 (trade name) Polystyrene-poly (ethylene 'butene) polystyrene block copolymer
[製造例 1]  [Production Example 1]
ハロゲン化ポリプロピレンの合成 Synthesis of halogenated polypropylene
特開 2002— 145944号公報記載の実施例に記載の方法に準じて合成したプロピ レン Z10—ゥンデセンー1 オール共重合体（Mw= 106,000、 Mn= 56,000、コ モノマー含量 0. 12mol%) 170gを、脱気窒素置換された 2Lガラス製反応器に入れ 、へキサン 1700ml、 2—ブロモイソ酪酸ブロミド 9. 2mlをそれぞれ添カ卩し、 60°Cで 2 時間加熱攪拌した。反応後、得られたスラリーをろ過後、減圧乾燥して 169. 5gの白 色固体状ポリマーを得た。 ^H— NMR分析から、 OH基の 94%が 2—ブロモイソ酪酸 基で修飾されたポリプロピレンであることが分力つた。 Propylene Z10-undecene-1-ol copolymer (Mw = 106,000, Mn = 56,000, copolymer) synthesized according to the method described in the examples described in JP-A-2002-145944 (Monomer content 0.12 mol%) 170 g was placed in a 2 L glass reactor purged with degassed nitrogen, and 1700 ml of hexane and 9.2 ml of 2-bromoisobutyric acid bromide were added, and heated at 60 ° C for 2 hours. Stir. After the reaction, the resulting slurry was filtered and dried under reduced pressure to obtain 169.5 g of a white solid polymer. ^ H—NMR analysis showed that 94% of the OH groups were polypropylene modified with 2-bromoisobutyric acid groups.
ポリプロピレンの数平均分子量、コモノマー含量、および 2—ブロモイソ酪酸基の修 飾割合力 計算したポリプロピレン一分子鎖当たりの 2—ブロモイソ酪酸基の数は 1. 5unitたった。  Number average molecular weight of polypropylene, comonomer content, and modification power of 2-bromoisobutyric acid group The number of 2-bromoisobutyric acid groups calculated per polypropylene molecular chain was 1.5 units.
[0247] [製造例 2] [0247] [Production Example 2]
ブロックポリマーの合成  Synthesis of block polymer
充分に窒素置換した内容積 2Lのガラス製反応器に、上記製造例 1で得たハロゲン 化ポリプロピレン 100gとスチレン（St) 786ml、アクリロニトリル (AN) 194mlを入れ、 25°Cで攪拌した。このスラリーに、臭化銅（I) 246mg、 PMDETA 0. 72mlをカロえ、 90°Cで 2時間重合を行った。反応液をろ過し、フィルター上の固体をメタノールで洗 浄後ポリマーを減圧乾燥して 161. 3gの固体状ポリマーを得た。得られたポリマー 5. 16gを取り、アセトン 150mlを用いてソクスレー抽出を還流下 9時間行った。抽出残を 減圧乾燥して 5. 07gのポリマー（以下、ブロックポリマー (A2—1)とする）を得た。抽 出後のサンプルの1 H— NMR分析より、 PPZStZANの組成比は、 63/26/11 ( wt%)であった。 100 g of the halogenated polypropylene obtained in Production Example 1, 786 ml of styrene (St) and 194 ml of acrylonitrile (AN) were placed in a 2 L glass reactor sufficiently purged with nitrogen, and stirred at 25 ° C. To this slurry, 246 mg of copper (I) bromide and 0.72 ml of PMDETA were prepared and polymerized at 90 ° C. for 2 hours. The reaction solution was filtered, the solid on the filter was washed with methanol, and the polymer was dried under reduced pressure to obtain 161.3 g of a solid polymer. 5.16 g of the polymer thus obtained was taken and Soxhlet extraction was performed using 150 ml of acetone for 9 hours under reflux. The extraction residue was dried under reduced pressure to obtain 5.07 g of a polymer (hereinafter referred to as block polymer (A2-1)). From the 1 H-NMR analysis of the sample after extraction, the composition ratio of PPZStZAN was 63/26/11 (wt%).
[0248] 組成比力 計算したブロックポリマー (A2— 1)のブロック (b)を構成する StZAN共 重合体の溶解度パラメータ一は 21. 9であった。組成比、ポリプロピレンの数平均分 子量、およびポリプロピレン一分子鎖当たりの 2—ブロモイソ酪酸基の数力 計算した ブロック（b)の分子量は 21,800であった。  [0248] Composition Specific Power The solubility parameter of the StZAN copolymer constituting the block (b) of the block polymer (A2-1) calculated was 21.9. The composition ratio, the number average molecular weight of polypropylene, and the number of 2-bromoisobutyric acid groups per polypropylene molecular chain were calculated. The molecular weight of block (b) was 21,800.
[0249] [製造例 3]  [0249] [Production Example 3]
ブロックポリマーの合成  Synthesis of block polymer
充分に窒素置換した内容積 2Lのガラス製反応器に、上記製造例 1で得たハロゲン 化ポリプロピレン 100gとメチルメタタリレート（MMA) 800ml,トルエン 200mlを入れ 、 25°Cで攪拌した。このスラリーに、臭化銅（I) 98mg、 PMDETA 0. 29mlをカロえ、 80°Cで 30分間重合を行った。反応液をろ過し、フィルター上の固体をメタノールで 洗浄後減圧乾燥して 158. 7gの固体状ポリマーを得た。得られたポリマー 4. 98gを 取り、アセトン 150mlを用いてソクスレー抽出を還流下 9時間行った。抽出残を減圧 乾燥して 4. 95gのポリマー（以下、ブロックポリマー (A2— 2)とする）を得た。抽出後 のサンプルの1 H— NMR分析より、 PPZPMMAの組成比は、 64/36 (wt%)であ つた o 100 g of the halogenated polypropylene obtained in Production Example 1 above, 800 ml of methyl metatalylate (MMA) and 200 ml of toluene were placed in a glass reactor having an internal volume of 2 L which had been sufficiently purged with nitrogen, and stirred at 25 ° C. To this slurry, add 98 mg of copper (I) bromide and 0.29 ml of PMDETA, Polymerization was carried out at 80 ° C for 30 minutes. The reaction solution was filtered, and the solid on the filter was washed with methanol and dried under reduced pressure to obtain 158.7 g of a solid polymer. 4.98 g of the obtained polymer was taken, and Soxhlet extraction was performed using 150 ml of acetone for 9 hours under reflux. The extraction residue was dried under reduced pressure to obtain 4.95 g of a polymer (hereinafter referred to as block polymer (A2-2)). From the 1 H-NMR analysis of the sample after extraction, the composition ratio of PPZPMMA was 64/36 (wt%).
[0250] 組成比から計算したブロックポリマー（A2— 2)のブロック（b)を構成する PMMAの 溶解度パラメータ一は 19. 1であった。組成比、ポリプロピレンの数平均分子量、およ びポリプロピレン一分子鎖当たりの 2—ブロモイソ酪酸基の数力 計算したブロック (b )の分子量は 21,000であった。  [0250] The solubility parameter of the PMMA constituting the block (b) of the block polymer (A2-2) calculated from the composition ratio was 19.1. The molecular weight of the block (b) calculated by the composition ratio, the number average molecular weight of polypropylene, and the number of 2-bromoisobutyric acid groups per polypropylene molecular chain was 21,000.
[0251] [製造例 4]  [0251] [Production Example 4]
ブロックポリマーの合成  Synthesis of block polymer
充分に窒素置換した内容積 2Lのガラス製反応器に、上記製造例 1で得たハロゲン 化ポリプロピレン 100gとスチレン（St) 873ml、 2—ヒドロキシェチルメタクリレート（HE MA) 80ml,トルエン 200mlを入れ、 25°Cで攪拌した。このスラリーに、臭化銅（1) 24 6mg、 PMDETAO. 72mlをカ卩え、 90°Cで 2時間重合を行った。反応液をろ過し、フ ィルター上の固体をメタノールで洗浄後減圧乾燥して 173gの固体状ポリマーを得た 。得られたポリマー 5. 10gを取り、アセトン 150mlを用いてソクスレー抽出を還流下 9 時間行った。抽出残を減圧乾燥して 4. 98gのポリマー（以下、ブロックポリマー (A2 —3)とする）を得た。抽出後のサンプルの1 H— NMR分析より、 PPZStZHEMAの 組成比は、 59Z37Z4(wt%)であった。 Into a 2 L glass reactor sufficiently purged with nitrogen, 100 g of the halogenated polypropylene obtained in Production Example 1 above, 873 ml of styrene (St), 80 ml of 2-hydroxyethyl methacrylate (HE MA), 200 ml of toluene, Stir at 25 ° C. To this slurry, 24 mg of copper (1) bromide and 72 ml of PMDETAO. Were added, and polymerization was carried out at 90 ° C. for 2 hours. The reaction solution was filtered, and the solid on the filter was washed with methanol and dried under reduced pressure to obtain 173 g of a solid polymer. 5. 10 g of the obtained polymer was taken, and Soxhlet extraction was performed using 150 ml of acetone for 9 hours under reflux. The extraction residue was dried under reduced pressure to obtain 4.98 g of a polymer (hereinafter referred to as block polymer (A2-3)). From the 1 H-NMR analysis of the sample after extraction, the composition ratio of PPZStZHEMA was 59Z37Z4 (wt%).
[0252] 組成比力 計算したブロックポリマー (A2— 3)のブロック (b)を構成する StZAN共 重合体の溶解度パラメータ一は 23. 1であった。組成比、ポリプロピレンの数平均分 子量、およびポリプロピレン一分子鎖当たりの 2—ブロモイソ酪酸基の数力 計算した ブロック（b)の分子量は 26,000であった。  [0252] Composition Specific Power The solubility parameter 1 of the StZAN copolymer constituting the block (b) of the block polymer (A2-3) calculated was 23.1. The composition ratio, the number average molecular weight of polypropylene, and the number of 2-bromoisobutyric acid groups per polypropylene molecular chain were calculated. The molecular weight of block (b) was 26,000.
[0253] [製造例 5]  [0253] [Production Example 5]
ブロックポリマーの合成  Synthesis of block polymer
充分に窒素置換した内容積 2Lのガラス製反応器に、上記製造例 1で得たハロゲン 化ポリプロピレン lOOgとスチレン（St) 720ml、アクリロニトリル (AN) 280ml、グリシジ ルメタタリレート（GMA) 60ml、トルエン 200mlを入れ、 25°Cで攪拌した。このスラリ 一に、臭化銅（I) 246mg、 PMDETA 0. 72mlをカ卩え、 90°Cで 2時間重合を行った 。反応液をろ過し、フィルター上の固体をメタノールで洗浄後減圧乾燥して 232. 6g の固体状ポリマーを得た。得られたポリマー 5. 03gを取り、アセトン 150mlを用いてソ タスレー抽出を還流下 9時間行った。抽出残を減圧乾燥して 4. 88gのポリマー（以下 、ブロックポリマー (A2— 4)とする）を得た。抽出後のサンプルの1 H— NMR分析より 、 PPZStZANZGMAの組成比は、 45Z3lZ2lZ3 (wt%)であった。 The halogen obtained in Production Example 1 above was placed in a 2 L glass reactor sufficiently purged with nitrogen. Polypropylene lOOg, styrene (St) 720 ml, acrylonitrile (AN) 280 ml, glycidyl methacrylate (GMA) 60 ml, toluene 200 ml were added and stirred at 25 ° C. To this slurry, 246 mg of copper (I) bromide and 0.72 ml of PMDETA were added, and polymerization was carried out at 90 ° C. for 2 hours. The reaction solution was filtered, and the solid on the filter was washed with methanol and dried under reduced pressure to obtain 232.6 g of a solid polymer. 5.03 g of the polymer thus obtained was taken and subjected to Sotasley extraction using 150 ml of acetone for 9 hours under reflux. The extraction residue was dried under reduced pressure to obtain 4.88 g of a polymer (hereinafter referred to as block polymer (A2-4)). From 1 H-NMR analysis of the sample after extraction, the composition ratio of PPZStZANZGMA was 45Z3lZ2lZ3 (wt%).
[0254] 組成比から計算したブロックポリマー（A2—4)のブロック（b)を構成する ASZGM A共重合体の溶解度パラメータ一は 22. 2であった。組成比、ポリプロピレンの数平 均分子量、およびポリプロピレン一分子鎖当たりの 2—ブロモイソ酪酸基の数力 計 算したブロック（b)の分子量は 45,000であった。  [0254] The solubility parameter 1 of the ASZGM A copolymer constituting the block (b) of the block polymer (A2-4) calculated from the composition ratio was 22.2. The molecular weight of the block (b) calculated from the composition ratio, the number average molecular weight of polypropylene, and the number of 2-bromoisobutyric acid groups per one molecular chain of polypropylene was 45,000.
[0255] [製造例 6]  [0255] [Production Example 6]
ハロゲン化ポリプロピレンの合成  Synthesis of halogenated polypropylene
充分に窒素置換した内容積 2Lのガラス製反応器に、ポリプロピレン (プライムポリマ 一社 S^139P) 150gおよびクロ口ベンゼン 1500mlを入れ、 110°Cで 2時間加熱攪 拌した。その後、 N—プロモスクシンイミド 5gをカ卩えて 110°Cで 2時間スラリー状態で 反応を行った。反応液を 3Lのアセトン中に注ぎ、析出したポリマーを減圧乾燥して 1 47gの白色粉末状変性ポリプロピレンを得た。得られたポリマー中に含まれる臭素原 子の含有量は、イオンクロマトグラフィー分析力 0. 34wt%であった。また、該ポリマ 一の分子量（PP換算）を GPCにより測定したところ、 Mw= 98,300、 Mn= 25,600 であった。  Into a 2 L glass reactor sufficiently purged with nitrogen, 150 g of polypropylene (Prime Polymer Co., Ltd. S ^ 139P) and 1500 ml of black benzene were placed and stirred at 110 ° C for 2 hours. Thereafter, 5 g of N-promosuccinimide was added, and the reaction was performed in a slurry state at 110 ° C. for 2 hours. The reaction solution was poured into 3 L of acetone, and the precipitated polymer was dried under reduced pressure to obtain 147 g of white powdery modified polypropylene. The content of bromine atoms contained in the obtained polymer was an ion chromatography analytical power of 0.34 wt%. The molecular weight (in terms of PP) of the polymer was measured by GPC and found to be Mw = 98,300 and Mn = 25,600.
[0256] ポリプロピレンの分子量および臭素原子の含有量力 計算したポリプロピレン一分 子鎖あたりの臭素原子のグラフト数は 1. 09unitだった。  [0256] The molecular weight of polypropylene and the content of bromine atoms The calculated number of bromine atoms grafted per polypropylene molecular chain was 1.09 units.
[0257] [製造例 7] [0257] [Production Example 7]
ブロックポリマーの合成  Synthesis of block polymer
充分に窒素置換した内容積 2Lのガラス製反応器に、上記製造例 6で得たハロゲン 変性ポリプロピレン 100gと St778ml、 AN192mlを入れ、 25°Cで攪拌した。このスラ リーに、臭化銅（I) 1033mg、 PMDETA3. Olmlをカ卩え、 85°Cで 4時間重合を行つ た。反応液をろ過し、フィルター上の固体をメタノールで洗浄後ポリマーを減圧乾燥 して 143. lgの固体状ポリマー（以下、ブロックポリマー (A2— 5)とする）を得た。 ¾ — NMR分析より、 PPZStZANの組成比は、 70Z2lZ9 (wt%)であった。 100 g of the halogen-modified polypropylene obtained in Production Example 6 above, St778 ml, and AN192 ml were placed in a 2 L glass reactor sufficiently purged with nitrogen, and stirred at 25 ° C. This slurry Li was charged with 1033 mg of copper (I) bromide and PMDETA 3. Olml, and polymerization was carried out at 85 ° C. for 4 hours. The reaction solution was filtered, the solid on the filter was washed with methanol, and the polymer was dried under reduced pressure to obtain 143. lg of solid polymer (hereinafter referred to as block polymer (A2-5)). ¾ — From the NMR analysis, the composition ratio of PPZStZAN was 70Z2lZ9 (wt%).
[0258] 組成比力 計算したブロックポリマー (A2— 5)のブロック (b)を構成する StZAN共 重合体の溶解度パラメータ一は 21. 8であった。組成比、ポリプロピレンの数平均分 子量、およびポリプロピレン一分子鎖当たりの臭素原子のグラフト数力 計算したプロ ック（b)の分子量は 10,200であった。  [0258] Compositional power The calculated solubility parameter of the StZAN copolymer constituting the block (b) of the block polymer (A2-5) was 21.8. The molecular weight of the block (b) calculated by the composition ratio, the number average molecular weight of polypropylene, and the number of grafts of bromine atoms per polypropylene molecular chain was 10,200.
[0259] 上記製造例におけるポリマー組成、ラジカル重合セグメントの溶解度パラメータ、セ グメント分子量等を表 1にまとめて示す。  [0259] Table 1 summarizes the polymer composition, the solubility parameter of the radical polymerization segment, the segment molecular weight, and the like in the above production example.
[0260] [表 1] [0260] [Table 1]
Figure imgf000075_0001
Figure imgf000075_0001
[製造例 8] [Production Example 8]
ハロゲン化ポリプロピレンの合成 Synthesis of halogenated polypropylene
特開 2002— 145944号公報の実施例に記載の方法に準じて製造したプロピレン /10—ゥンデセン— 1—オール共重合ポリマーを、ガラス製反応器に入れ、ポリマー 濃度が lOOgZLになるよう、へキサンを加えスラリー状態にした。ポリマーに存在する 水酸基の量に対し、 5倍当量の 2—ブロモイソ酪酸ブロミド添カ卩し、 60°Cに昇温し、 3 時間加熱撹拌した。反応液を、 20°CZhの冷却速度で 20°Cまで冷却し、ポリマーを 濾別した。ポリマーを、再度アセトンに入れ 10分間攪拌することで固液洗浄した後に 再度濾取した。得られた白色ポリマーを 50°C、 lOTorrの減圧条件下で 10時間乾燥 させた。高温 GPC分析の結果、ポリプロピレン換算重量平均分子量 Mw= 106,000 、ポリプロピレン換算数平均分子量 Mn= 56,400であり、 DSCの測定結果より融点 力 S154°Cであり、 — NMR分析より、 2—ブロモイソ酪酸ブロミド由来の臭素が導入 された末端が平均導入本数として 1. 9本 Z鎖であった。 NMRの結果、水酸基 の 94%が 2—ブロモイソ酪酸基で修飾されたハロゲン化ポリプロピレンであった。 ブロックポリマーの合成 Propylene produced according to the method described in Examples of JP-A-2002-145944 The / 10-undecene-1-ol copolymer was placed in a glass reactor, and hexane was added to form a slurry so that the polymer concentration was lOOgZL. A 5-fold equivalent of 2-bromoisobutyric acid bromide was added to the amount of hydroxyl groups present in the polymer, the temperature was raised to 60 ° C., and the mixture was heated and stirred for 3 hours. The reaction solution was cooled to 20 ° C. at a cooling rate of 20 ° C. Zh, and the polymer was filtered off. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then filtered again. The obtained white polymer was dried at 50 ° C. under reduced pressure of lOTorr for 10 hours. As a result of high temperature GPC analysis, polypropylene equivalent weight average molecular weight Mw = 106,000, polypropylene equivalent number average molecular weight Mn = 56,400, DSC measurement result shows melting point power S154 ° C, — From NMR analysis, derived from 2-bromoisobutyric acid bromide The average number of bromine introduced ends was 1.9 Z-chains. As a result of NMR, 94% of the hydroxyl groups were halogenated polypropylene modified with 2-bromoisobutyric acid groups. Synthesis of block polymer
ノ、ロゲン化ポリプロピレンをガラス製重合器に入れ、スチレン (St)とアクリロニトリル ( AN)がそれぞれ 4. 9M、 2. 1Mになるように調製したトルエン溶液を、ポリマー濃度 力 S93gZLになるように加え、窒素パブリングによる脱酸素操作を行った。その後、臭 化銅（I)： N,N,N',N",N"—ペンタメチルジェチレントリアミン（以下「PMDETA」と 略記する。）の 1： 2 (mol比）のトルエン溶液をノヽロゲン化ポリプロピレンのハロゲン含 有量に対し、 2当量の臭ィ匕銅 (I)となるように加え、加温 '攪拌した。 105°Cで 2. 5時 間重合したところで、氷浴で冷却し、ポリマー混合液を濾過し、濾紙上のポリマーをメ タノールで洗浄した。得られたポリマーを減圧下、 80°Cで乾燥することで白色のポリ マー（以下、ブロックポリマー (A2— 6)とする）を得た。  Rogenized polypropylene is placed in a glass polymerizer, and a toluene solution prepared so that styrene (St) and acrylonitrile (AN) are 4.9M and 2.1M, respectively, is added so that the polymer concentration is S93gZL. Then, deoxygenation operation was performed by nitrogen publishing. After that, a 1: 2 (mol ratio) toluene solution of copper bromide (I): N, N, N ', N ", N" -pentamethylgerylenetriamine (hereinafter abbreviated as "PMDETA") was used. To the halogen content of the rogenized polypropylene, 2 equivalents of odorous copper (I) were added and heated and stirred. After 2.5 hours of polymerization at 105 ° C, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (A2-6)).
[製造例 9]  [Production Example 9]
ハロゲン化ポリプロピレンの合成 Synthesis of halogenated polypropylene
特開 2002— 145944号公報の実施例に記載の方法に準じて製造したプロピレン /10—ゥンデセン— 1—オール共重合ポリマーを、ガラス製反応器に入れ、ポリマー 濃度が lOOgZLになるよう、へキサンを加えスラリー状態にした。ポリマーに存在する 水酸基の量に対し、 5倍当量の 2—ブロモイソ酪酸ブロミド添カ卩し、 60°Cに昇温し、 3 時間加熱撹拌した。反応液を、 20°CZhの冷却速度で 20°Cまで冷却し、ポリマーを 濾別した。ポリマーを、再度アセトンに入れ 10分間攪拌することで固液洗浄した後に 再度濾取した。得られた白色ポリマーを 50°C、 lOTorrの減圧条件下で 10時間乾燥 させた。高温 GPC分析の結果、ポリプロピレン換算重量平均分子量 Mw= 82,800、 ポリプロピレン換算数平均分子量 Mn=41, 300であり、 DSCの測定結果より融点が 154°Cであり、 NMR分析より、 2 ブロモイソ酪酸ブロミド由来の臭素が導入さ れた末端が平均導入本数として 1. 3本 Z鎖であった。 NMRの結果、水酸基の 97%が 2 ブロモイソ酪酸基で修飾されたハロゲン化ポリプロピレンであった。 A propylene / 10-undecene-1-ol copolymer produced according to the method described in the examples of JP-A-2002-145944 is placed in a glass reactor, and hexane is added so that the polymer concentration becomes lOOgZL. Was added to form a slurry. A 5-fold equivalent of 2-bromoisobutyric acid bromide was added to the amount of hydroxyl groups present in the polymer, the temperature was raised to 60 ° C., and the mixture was heated and stirred for 3 hours. Cool the reaction solution to 20 ° C at a cooling rate of 20 ° C Zh, Filtered off. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then filtered again. The obtained white polymer was dried at 50 ° C. under reduced pressure of lOTorr for 10 hours. As a result of high temperature GPC analysis, polypropylene equivalent weight average molecular weight Mw = 82,800, polypropylene equivalent number average molecular weight Mn = 41,300, DSC measurement result shows melting point is 154 ° C, NMR analysis shows that it is derived from 2-bromoisobutyric acid bromide The average number of bromine introduced ends was 1.3 Z chains. As a result of NMR, 97% of the hydroxyl groups were halogenated polypropylene modified with 2 bromoisobutyric acid groups.
ブロックポリマーの合成  Synthesis of block polymer
得られたハロゲンィ匕ポリプロピレンをガラス製重合器に入れ、スチレンモノマーを、 ポリマー濃度が 189gZLになるように加え、窒素パブリングによる脱酸素操作を行つ た。その後、臭化銅（I)： PMDETAの 1 : 2 (mol比）のトルエン溶液をハロゲン化ポリ プロピレンのハロゲン含有量に対し、 1. 5当量の臭ィ匕銅 (I)となるようにカ卩ぇ、加温' 攪拌した。 100°Cで 5時間重合したところで、氷浴で冷却し、ポリマーを析出させた後 、濾過し、メタノールで洗浄した。得られたポリマーを減圧下（10Torr)、 80°Cで乾燥 することで白色のポリマーを得た（以下、ブロックポリマー (A2 - 7)とする）。  The obtained halogenated polypropylene was put into a glass polymerization vessel, styrene monomer was added so that the polymer concentration was 189 gZL, and deoxygenation operation was performed by nitrogen publishing. Then, a copper solution of copper bromide (I): PMDETA in a 1: 2 (molar ratio) toluene solution was added to give 1.5 equivalents of odorous copper (I) to the halogen content of the halogenated polypropylene. Yeah, warm up 'stir. When the polymerization was carried out at 100 ° C. for 5 hours, the mixture was cooled in an ice bath to precipitate a polymer, filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (10 Torr) to obtain a white polymer (hereinafter referred to as block polymer (A2-7)).
[0263] [製造例 10]  [0263] [Production Example 10]
ブロックポリマーの合成  Synthesis of block polymer
製造例 8に記載の方法で合成されたハロゲンィ匕ポリプロピレンをガラス製重合器に 入れ、アクリル酸 n ブチル（nBA)とメタクリル酸メチル（MMA)がそれぞれ 1. 1 M、 0. 1Mになるように調製したトルエン溶液を、ポリマー濃度が 30g/Lになるよう に加え、窒素パブリングによる脱酸素操作を行った。その後、臭化銅 (I)： PMDETA の 1： 2 (mol比）のトルエン溶液をハロゲン化ポリプロピレンのハロゲン含有量に対し、 3. 5等量の臭ィ匕銅 (I)となるように加え、加温 '攪拌した。 105°Cで 9時間重合したとこ ろで、氷浴で冷却し、ポリマー混合液を濾過し、濾紙上のポリマーをメタノールで洗浄 した。得られたポリマーを減圧下、 80°Cで乾燥することで白色のブロック共重合体を 得た（以下、ブロックポリマー (A2— 8)とする）。  Put the halogenated polypropylene synthesized by the method described in Production Example 8 into a glass polymerizer so that n-butyl acrylate (nBA) and methyl methacrylate (MMA) are 1.1 M and 0.1 M, respectively. The prepared toluene solution was added so that the polymer concentration became 30 g / L, and deoxygenation operation was performed by nitrogen publishing. Then, add a 1: 2 (mol ratio) toluene solution of copper bromide (PM): PMDETA to 3.5 equivalents of odorous copper (I) to the halogen content of the halogenated polypropylene. Warm, stir. After polymerization at 105 ° C for 9 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white block copolymer (hereinafter referred to as block polymer (A2-8)).
[0264] [製造例 11]  [0264] [Production Example 11]
ブロックポリマーの合成 製造例 8に記載の方法で合成されたハロゲンィ匕ポリプロピレンをガラス製重合器に 入れ、スチレン（St)、アクリロニトリル (AN)及びメタクリル酸グリシジル (GMA)がそ れぞれ 4. 6M、 2. OM、 0. 7Mとなるように調製したトルエン溶液を、ポリマー濃度が 86gZLとなるように加え、窒素パブリングによる脱酸素操作を行った。その後、臭化 銅（I)： PMDETAの 1： 2 (mol比）のトルエン溶液をハロゲン化ポリプロピレンのハロ ゲン含有量に対し、 1. 5当量の臭ィ匕銅 (I)となるようにカ卩え、加温'攪拌した。 80°Cで 1.5時間重合したところで、氷浴で冷却し、ポリマー混合液を濾過し、濾紙上のポリマ 一をメタノールで洗浄した。得られたポリマーを減圧下、 80°Cで乾燥することで白色 のポリマーを得た（以下、ブロックポリマー (A2 - 9)とする）。 Synthesis of block polymer Halogenated polypropylene synthesized by the method described in Production Example 8 was placed in a glass polymerizer, and styrene (St), acrylonitrile (AN), and glycidyl methacrylate (GMA) were 4.6 M and 2. OM, respectively. The toluene solution prepared to 0.7 M was added so that the polymer concentration became 86 gZL, and deoxygenation operation was performed by nitrogen publishing. Thereafter, a 1: 2 (mol ratio) toluene solution of copper (I) bromide: PMDETA was added to the halogen content of the halogenated polypropylene to give 1.5 equivalents of odorous copper (I). Barking, warming 'stirring. After polymerization at 80 ° C. for 1.5 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (A2-9)).
[0265] [製造例 12] [0265] [Production Example 12]
ブロックポリマーの合成  Synthesis of block polymer
製造例 8に記載の方法で合成されたハロゲンィ匕ポリプロピレンをガラス製重合器に 入れ、アクリル酸 n ブチル（nBA)とメタクリル酸グリシジル（GMA)がそれぞれ 3 . OM、0. 30Mになるように調製したトルエン溶液を、ポリマー濃度が 93g/Lになる ように加え、窒素パブリングによる脱酸素操作を行った。その後、臭化銅 (I)： PMDE TAの 1： 2 (mol比）のトルエン溶液をノヽロゲン化ポリプロピレンのハロゲン含有量に対 し、 2当量の臭ィ匕銅 (I)となるようにカ卩え、加温 '攪拌した。 75°Cで 1時間重合したとこ ろで、氷浴で冷却し、ポリマー混合液を濾過し、濾紙上のポリマーをメタノールで洗浄 した。得られたポリマーを減圧下、 80°Cで乾燥することで白色のポリマーを得た (以 下、ブロックポリマー（A2— 10)とする）。  Halogenated polypropylene synthesized by the method described in Production Example 8 is placed in a glass polymerizer and prepared so that n-butyl acrylate (nBA) and glycidyl methacrylate (GMA) are 3. OM and 0.30 M, respectively. The toluene solution was added to a polymer concentration of 93 g / L, and deoxygenation was performed by nitrogen publishing. After that, a 1: 2 (mol ratio) toluene solution of copper (I) bromide: PMDE TA was added to the halogen content of the halogenated polypropylene to give 2 equivalents of odorous copper (I). Barking, warming 'stirring. After polymerization at 75 ° C. for 1 hour, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (A2-10)).
[0266] [製造例 13] [0266] [Production Example 13]
ブロックポリマーの合成  Synthesis of block polymer
製造例 8に記載の方法で合成されたハロゲンィ匕ポリプロピレンをガラス製重合器に 入れ、スチレン（St)及びメタクリル酸メチル（MMA)がそれぞれ 5. 9M、0. 6Mとな るように調製したトルエン溶液を、ポリマー濃度が 87gZLとなるようにカ卩え、窒素パブ リングによる脱酸素操作を行った。その後、臭化銅 (I)： PMDETAの 1 : 2 (mol比）の トルエン溶液をハロゲン化ポリプロピレンのハロゲン含有量に対し、 2. 0当量の臭化 銅 (I)となるように加え、加温 '攪拌した。 80°Cで 6. 0時間重合したところで、氷浴で 冷却し、ポリマー混合液を濾過し、濾紙上のポリマーをメタノールで洗浄した。得られ たポリマーを減圧下、 80°Cで乾燥することで白色のポリマーを得た (以下、ブロックポ リマー (A2— 11)とする）。 Toluene prepared by adding the halogenated polypropylene synthesized by the method described in Production Example 8 to a glass polymerization vessel so that styrene (St) and methyl methacrylate (MMA) were 5.9M and 0.6M, respectively. The solution was prepared so that the polymer concentration became 87 gZL, and deoxygenation was performed by nitrogen publishing. Then, add a 1: 2 (mol ratio) toluene solution of copper (I) bromide: PMDETA to 2.0 equivalents of copper (I) bromide with respect to the halogen content of the halogenated polypropylene. Warm 'stirred. When polymerized at 80 ° C for 6.0 hours, in an ice bath After cooling, the polymer mixture was filtered and the polymer on the filter paper was washed with methanol. The resulting polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (A2-11)).
[0267] [製造例 14] [0267] [Production Example 14]
ブロックポリマーの合成  Synthesis of block polymer
製造例 8に記載の方法で合成されたハロゲンィ匕ポリプロピレンをガラス製重合器に 入れ、スチレン（St)及びメタクリル酸メチル（MMA)がそれぞれ 5. 9M、 1. 2Mとな るように調製したトルエン溶液を、ポリマー濃度が 87gZLとなるようにカ卩え、窒素パブ リングによる脱酸素操作を行った。その後、臭化銅 (I)： PMDETAの 1 : 2 (mol比）の トルエン溶液をハロゲン化ポリプロピレンのハロゲン含有量に対し、 2. 0当量の臭化 銅 (I)となるように加え、加温 '攪拌した。 80°Cで 4. 5時間重合したところで、氷浴で 冷却し、ポリマー混合液を濾過し、濾紙上のポリマーをメタノールで洗浄した。得られ たポリマーを減圧下、 80°Cで乾燥することで白色のポリマーを得た (以下、ブロックポ リマー（A2— 12)とする）。  Toluene prepared by adding the halogenated polypropylene synthesized by the method described in Production Example 8 to a glass polymerization vessel so that styrene (St) and methyl methacrylate (MMA) were 5.9M and 1.2M, respectively. The solution was prepared so that the polymer concentration became 87 gZL, and deoxygenation was performed by nitrogen publishing. Then, add a 1: 2 (mol ratio) toluene solution of copper (I) bromide: PMDETA to 2.0 equivalents of copper (I) bromide with respect to the halogen content of the halogenated polypropylene. Warm 'stirred. After polymerization at 80 ° C. for 4.5 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as block polymer (A2-12)).
[0268] [製造例 15]  [0268] [Production Example 15]
ブロックポリマーの合成  Synthesis of block polymer
製造例 8に記載の方法で合成されたハロゲンィ匕ポリプロピレンをガラス製重合器に 入れ、スチレン（St)及びメタクリル酸メチル（MMA)がそれぞれ 5. 9M、 1. 8Mとな るように調製したトルエン溶液を、ポリマー濃度が 87gZLとなるようにカ卩え、窒素パブ リングによる脱酸素操作を行った。その後、臭化銅 (I)： PMDETAの 1 : 2 (mol比）のト ルェン溶液をノヽロゲン化ポリプロピレンのハロゲン含有量に対し、 2. 0当量の臭化銅 (I)となるように加え、加温 '攪拌した。 80°Cで 3. 0時間重合したところで、氷浴で冷 却し、ポリマー混合液を濾過し、濾紙上のポリマーをメタノールで洗浄した。得られた ポリマーを減圧下、 80°Cで乾燥することで白色のポリマーを得た（以下、ブロックポリ マー (A2— 13)とする）。各種モノマーの組成及びラジカル重合セグメントの溶解度 ノ メータ及びセグメント分子量を表 2にまとめた。  Toluene prepared by adding the halogenated polypropylene synthesized by the method described in Production Example 8 to a glass polymerization vessel so that styrene (St) and methyl methacrylate (MMA) were 5.9M and 1.8M, respectively. The solution was prepared so that the polymer concentration became 87 gZL, and deoxygenation was performed by nitrogen publishing. Then, add a 1: 2 (mol ratio) toluene solution of copper (I) bromide: PMDETA to 2.0 equivalents of copper bromide (I) with respect to the halogen content of the halogenated polypropylene. Warm, stir. When polymerization was performed at 80 ° C. for 3.0 hours, the mixture was cooled in an ice bath, the polymer mixture was filtered, and the polymer on the filter paper was washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure to obtain a white polymer (hereinafter referred to as a block polymer (A2-13)). Table 2 summarizes the composition of various monomers and the radical polymerization segment solubility meter and segment molecular weight.
[0269] 上記製造例 8〜 15におけるポリマー組成、ラジカル重合セグメントの溶解度パラメ ータ、セグメント分子量等を表 2にまとめて示す。 表 2 [0269] Table 2 summarizes the polymer compositions, radical polymerization segment solubility parameters, segment molecular weights, etc. in Production Examples 8 to 15 above. Table 2
Figure imgf000080_0001
Figure imgf000080_0001
0270 [0271] [製造例 16] 0270 [0271] [Production Example 16]
ブロックポリマーの合成  Synthesis of block polymer
充分に窒素置換した内容積 2Lのガラス製反応器に、上記製造例 1で得たハロゲン 化ポリプロピレン lOOgとスチレン（St) 547mlを入れ、 25°Cで攪拌した。このスラリー に、臭化銅（I) 246mg、 PMDETA 0. 72mlをカ卩え、 105°Cで 5時間重合を行った。 反応液をろ過し、フィルター上の固体をメタノールで洗浄後ポリマーを減圧乾燥して 1 32. 7gの固体状ポリマーを得た。得られたポリマー 5. 16gを取り、アセトン 150mlを 用いてソクスレー抽出を還流下 9時間行った。抽出残を減圧乾燥して 5. 07gのポリマ 一を得た。抽出後のサンプルの1 H— NMR分析より、 PP/Stの組成比は、 76Z24 ( wt比）であった。 Into a 2 L glass reactor sufficiently purged with nitrogen, the halogenated polypropylene lOOg obtained in Production Example 1 and 547 ml of styrene (St) were placed and stirred at 25 ° C. To this slurry, 246 mg of copper (I) bromide and 0.72 ml of PMDETA were added, and polymerization was carried out at 105 ° C. for 5 hours. The reaction solution was filtered, and the solid on the filter was washed with methanol, and then the polymer was dried under reduced pressure to obtain 132.7 g of solid polymer. 5.16 g of the polymer obtained was taken, and Soxhlet extraction was performed for 9 hours under reflux using 150 ml of acetone. The extraction residue was dried under reduced pressure to obtain 5.07 g of a polymer. From the 1 H-NMR analysis of the sample after extraction, the composition ratio of PP / St was 76Z24 (wt ratio).
[0272] 組成比力 計算したブロックポリマー (A2— 14)のブロック (b)を構成する St重合体 の溶解度パラメータ一は 18. 7であった。組成比、ポリプロピレンの数平均分子量、 およびポリプロピレン一分子鎖当たりの 2—ブロモイソ酪酸基の数力 計算したブロッ ク（b)の分子量は 11, 700であった。  [0272] The specific solubility parameter of the St polymer constituting the block (b) of the block polymer (A2-14) calculated was 18.7. The molecular weight of block (b) calculated as composition ratio, number average molecular weight of polypropylene, and number power of 2-bromoisobutyric acid group per polypropylene molecular chain was 11,700.
[0273] [実施例 1] [0273] [Example 1]
ポリプロピレン (A1— 1) 66. 7重量部、製造例 2で製造したブロックポリマー (A2— 1) 4. 8重量部、ポリカーボネート (B1— 1) 28. 5重量部を、二軸押出機にて溶融混 練し、ペレット状のポリオレフイン榭脂組成物を調製した。得られたポリオレフイン榭脂 組成物を用いて、室温クロ口ホルム不溶成分量を測定した。また、射出成形機 (IS55 、東芝機械株式会社製)にて ASTM試験片を成形した。溶融混練条件および射出 成形条件を下記に、室温クロ口ホルム不溶成分中に含まれるブロック (b)に由来する 成分の含有量 (以下、ブロック (b)含有量とする）および成形品の物性を表 3に示す。  Polypropylene (A1-1) 66. 7 parts by weight, block polymer prepared in Production Example 2 (A2-1) 4. 8 parts by weight, polycarbonate (B1-1) 28.5 parts by weight in a twin screw extruder The mixture was melt-kneaded to prepare a pellet-shaped polyolefin resin composition. Using the obtained polyolefin resin composition, the amount of room-temperature black mouth form insoluble component was measured. In addition, ASTM test pieces were molded with an injection molding machine (IS55, manufactured by Toshiba Machine Co., Ltd.). The melt kneading conditions and injection molding conditions are shown below. The content of the component derived from the block (b) contained in the room-temperature chloroform-insoluble component (hereinafter referred to as the block (b) content) and the physical properties of the molded product are as follows. Table 3 shows.
[0274] <溶融混練条件 > [0274] <Melt-kneading conditions>
同方向二軸混練機：品番 KZW15— 30HG、株式会社テクノベル製  Same-direction twin-screw kneader: Product number KZW15-30HG, manufactured by Technobel
混練温度： 240°C  Kneading temperature: 240 ° C
スクリュー回転数： 200rpm  Screw rotation speed: 200rpm
<射出成形条件 >  <Injection molding conditions>
射出成形機:品番 IS55、東芝機械株式会社製 シリンダー温度： 240°C Injection molding machine: Part number IS55, manufactured by Toshiba Machine Co., Ltd. Cylinder temperature: 240 ° C
金型温度： 60°C  Mold temperature: 60 ° C
[実施例 2〜14]  [Examples 2 to 14]
ポリオレフイン、ォレフィン系ブロック共重合体およびポリカーボネート榭脂の種類お よび量、溶融混練時の混練温度および射出成形時のシリンダー温度を表 3または 4 に記載のように変更した以外は実施例 1と同様にして ASTM試験片を成形した。クロ 口ホルム不溶成分量及び成形品の物性を表 3、 4に示す。  Example 1 except that the types and amounts of polyolefin, olefin-based block copolymer and polycarbonate resin, the kneading temperature during melt kneading and the cylinder temperature during injection molding were changed as shown in Table 3 or 4. An ASTM test piece was molded. Tables 3 and 4 show the amount of insoluble component in the mouthpiece and the physical properties of the molded product.
[0275] [比較例 1〜4] [0275] [Comparative Examples 1 to 4]
ポリオレフインおよびポリカーボネート榭脂の種類および量、溶融混練時の混練温 度および射出成形時のシリンダー温度を表 4に記載のように変更し、かつォレフィン 系ブロック共重合体を使用しな力つた以外は実施例 1と同様にして ASTM試験片を 成形した。ブロック (b)含有量及び成形品の物性を表 4に示す。  Except that the types and amounts of polyolefin and polycarbonate resin, the kneading temperature during melt kneading and the cylinder temperature during injection molding were changed as shown in Table 4, and olefin-based block copolymers were used. ASTM test specimens were molded in the same manner as in Example 1. Table 4 shows the content of block (b) and the physical properties of the molded product.
[0276] [比較例 5〜7] [0276] [Comparative Examples 5 to 7]
ポリオレフインおよびポリカーボネート榭脂の種類および量、溶融混練時の混練温 度および射出成形時のシリンダー温度を表 4に記載のように変更し、かつ上記製造 例で製造したォレフィン系ブロック共重合体に代えて表 4に記載のォレフィン系ブロッ ク共重合体を表 4に記載した量使用した以外は実施例 1と同様にして ASTM試験片 を成形した。ブロック (b)含有量及び成形品の物性を表 4に示す。  The types and amounts of polyolefin and polycarbonate resin, the kneading temperature during melt kneading and the cylinder temperature during injection molding were changed as shown in Table 4 and replaced with the olefin block copolymer produced in the above production example. An ASTM test piece was molded in the same manner as in Example 1 except that the olefin-based block copolymer shown in Table 4 was used in the amount shown in Table 4. Table 4 shows the content of block (b) and the physical properties of the molded product.
[0277] [実施例 15] [Example 15]
ポリプロピレン (A1— 1) 28. 5重量部、製造例 2で製造したブロックポリマー (A2— 1) 4. 8重量部、ポリカーボネート (B1— 1) 66. 7重量部を、二軸押出機にて溶融混 練し、ペレット状のポリオレフイン榭脂組成物を調製した。得られたポリオレフイン榭脂 組成物を用いて、射出成形機 (IS55、東芝機械株式会社製）にて ASTM試験片を 成形した。ノッチを機械加工したアイゾット試験片を室温でアセトンもしくはキシレン溶 媒中に 48時間浸漬し、浸漬前後のアイゾット衝撃強度を測定した。混練温度'成形 温度、及び測定結果を表 5に示す。浸漬後と浸漬前とのアイゾット衝撃強度の比率を 取り、保持率とした。保持率が 100%に近いほど、浸漬前の物性に近ぐ耐溶剤性に 優れることを示す。 [0278] [比較例 8〜9] Polypropylene (A1-1) 28.5 parts by weight, block polymer prepared in Production Example 2 (A2-1) 4. 8 parts by weight, polycarbonate (B1-1) 66. 7 parts by weight in a twin screw extruder The mixture was melt-kneaded to prepare a pellet-shaped polyolefin resin composition. Using the obtained polyolefin resin composition, an ASTM test piece was molded with an injection molding machine (IS55, manufactured by Toshiba Machine Co., Ltd.). Izod specimens with machined notches were immersed in acetone or xylene solvent for 48 hours at room temperature, and Izod impact strength before and after immersion was measured. Table 5 shows the kneading temperature, the molding temperature, and the measurement results. The ratio of Izod impact strength after immersion and before immersion was taken as the retention rate. The closer the retention rate is to 100%, the better the solvent resistance, which is close to the physical properties before immersion. [0278] [Comparative Examples 8 to 9]
ポリオレフインおよびポリカーボネート榭脂の量、溶融混練時の混練温度および射 出成形時のシリンダー温度を表 5に記載のように変更し、かつ上記製造例 2で製造し たォレフイン系ブロック共重合体 (A2— 1)を使用しない以外は実施例 15と同様にし て ASTM試験片を成形した。実施例 15と同様に溶媒浸漬前後のアイゾット衝撃強 度を測定した。測定結果を表 5に示す。  The amount of polyolefin and polycarbonate resin, the kneading temperature at the time of melt kneading and the cylinder temperature at the time of injection molding were changed as shown in Table 5, and the polyolefin block copolymer produced in Production Example 2 (A2 — ASTM test pieces were molded in the same manner as in Example 15 except that 1) was not used. In the same manner as in Example 15, Izod impact strength before and after immersion in the solvent was measured. Table 5 shows the measurement results.
[0279] [表 3] [0279] [Table 3]
表 3 Table 3
Figure imgf000084_0001
Figure imgf000084_0001
表 4 Table 4
Figure imgf000085_0001
Figure imgf000085_0001
§¾〕 _〕804 表 5] §¾] _] 804 Table 5]
Figure imgf000086_0001
Figure imgf000086_0001
[実施例 16] [Example 16]
ポリプロピレン (Al— 1) 210重量部、ポリプロピレン (A1— 3) 45重量部、製造例 3 で製造したブロックポリマー (A2— 2) 15重量部、アクリル系榭脂（B2— 1) 90重量部 を、二軸押出機にて溶融混練し、ペレット状のポリオレフイン樹脂組成物を調製した。 得られたポリオレフイン榭脂組成物を用いて、室温クロ口ホルム不溶成分量を測定し た。また、射出成形機 (IS55、東芝機械株式会社製）にて ASTM試験片を成形した 。溶融混練条件および射出成形条件は実施例 1と同じである。室温クロ口ホルム不溶 成分中に含まれるブロック (b)に由来する成分の含有量 (以下、ブロック (b)含有量と する）および成形品の物性を表 6に示す。 210 parts by weight of polypropylene (Al-1), 45 parts by weight of polypropylene (A1-3), 15 parts by weight of the block polymer (A2-2) produced in Production Example 3, 90 parts by weight of acrylic resin (B2-1) Then, the mixture was melt-kneaded with a twin-screw extruder to prepare a pellet-shaped polyolefin resin composition. Using the obtained polyolefin resin composition, the amount of insoluble components at room temperature was measured. In addition, an ASTM test piece was molded with an injection molding machine (IS55, manufactured by Toshiba Machine Co., Ltd.). The melt-kneading conditions and injection molding conditions are the same as in Example 1. Insoluble at room temperature Table 6 shows the content of the component derived from block (b) contained in the component (hereinafter referred to as block (b) content) and the physical properties of the molded product.
[0283] [比較例 10] [0283] [Comparative Example 10]
ブロックポリマー (A2— 2)を使用しな力つたこと以外は実施例 16と同様にして AST AST was performed in the same manner as in Example 16 except that the block polymer (A2-2) was used.
M試験片を成形した。ブロック (b)含有量及び成形品の物性を表 6に示す。 M test pieces were molded. Table 6 shows the content of block (b) and the physical properties of the molded product.
[0284] [表 6] [0284] [Table 6]
Figure imgf000087_0001
Figure imgf000087_0001
[0285] [実施例 17] [0285] [Example 17]
ポリプロピレン (Al— 1) 66. 7重量部、製造例 8で製造したブロックポリマー (A2— 6) 4. 8重量部、ビニル重合体 (B3— 1) 28. 5重量部を、二軸押出機にて溶融混練 し、ペレット状のポリオレフイン榭脂組成物を調製した。得られたポリオレフイン榭脂組 成物を用いて、室温クロ口ホルム不溶成分量を測定した。さらに得られたポリオレフィ ン榭脂組成物を 80°Cの減圧乾燥機で一晩乾燥して、射出成形機にて ASTM試験 片を成形した。溶融混練条件および射出成形条件を下記に、成形品の物性を表 7に 示す。 Polypropylene (Al— 1) 66. 7 parts by weight, block polymer produced in Production Example 8 (A2— 6) 4.8 parts by weight and 28.5 parts by weight of vinyl polymer (B3-1) were melt-kneaded in a twin screw extruder to prepare a pelleted polyolefin resin composition. The amount of insoluble components at room temperature was measured using the obtained polyolefin resin composition. Further, the obtained polyolefin resin composition was dried overnight in a vacuum dryer at 80 ° C., and an ASTM test piece was molded using an injection molding machine. The melt-kneading conditions and injection molding conditions are shown below, and the physical properties of the molded products are shown in Table 7.
[0286] <溶融混練条件 >  [0286] <Melting and kneading conditions>
同方向二軸混練機：品番 KZW15— 30HG、株式会社テクノベル製  Same-direction twin-screw kneader: Product number KZW15-30HG, manufactured by Technobel
混練温度： 200°C  Kneading temperature: 200 ° C
スクリュー回転数： 200rpm  Screw rotation speed: 200rpm
<射出成形条件 >  <Injection molding conditions>
射出成形機:品番 IS55、東芝機械株式会社製  Injection molding machine: Part number IS55, manufactured by Toshiba Machine Co., Ltd.
シリンダー温度： 200°C  Cylinder temperature: 200 ° C
金型温度 ：30°C  Mold temperature: 30 ° C
[実施例 18〜27]  [Examples 18 to 27]
ポリオレフイン、ブロックポリマーおよびビュル重合体の種類および量を変更した以 外は実施例 17と同様にして ASTM試験片を成形した。成形品の物性を表 7、 8に示 す。  ASTM test specimens were molded in the same manner as in Example 17 except that the types and amounts of the polyolefin, block polymer, and bur polymer were changed. Tables 7 and 8 show the physical properties of the molded products.
[0287] [比較例 11〜19]  [0287] [Comparative Examples 11 to 19]
ポリオレフインおよびビュル重合体の種類および量を変更し、共重合体 H1043、 A 3400、 A3100を使用し、かつブロックポリマーを使用しなかった以外は実施例 17と 同様にして ASTM試験片を成形した。成形品の物性を表 7、 8に示す。  ASTM specimens were molded in the same manner as in Example 17 except that the types and amounts of polyolefin and bur polymers were changed, copolymers H1043, A3400, and A3100 were used, and no block polymer was used. Tables 7 and 8 show the physical properties of the molded products.
[0288] 表 7を見れば明らかなようにブロックポリマーを添加することにより、榭脂糸且成物の剛 性を低下させること無しに衝撃強度や引張伸びが向上することが分かる。共重合体 H1043を添加すると衝撃強度及び引張伸びは向上するものの、剛性が低下する。 また、表 8を見れば明らかなようにブロックポリマーを添加することにより、榭脂糸且成物 の剛性を低下させること無しに引張伸びが向上することが分かる。  As is apparent from Table 7, it can be seen that the addition of the block polymer improves the impact strength and the tensile elongation without reducing the rigidity of the cocoon yarn and the composition. Addition of copolymer H1043 improves impact strength and tensile elongation but decreases rigidity. In addition, as can be seen from Table 8, it can be seen that the addition of a block polymer improves the tensile elongation without reducing the rigidity of the greave yarn and the composition.
[0289] [表 7] 表 7 [0289] [Table 7] Table 7
Figure imgf000089_0001
Figure imgf000089_0001
(A21— (A21—
〔〕 si029__1w∞  [] Si029__1w∞
表 8  Table 8
Figure imgf000090_0002
Figure imgf000090_0002
Figure imgf000090_0001
Figure imgf000090_0001
〔〕〔像〕02908 4) 5重量部、ポリフエ-レンオキサイド (B4— 1) 30重量部を、二軸押出機にて溶融 混練し、ペレット状のポリオレフイン榭脂組成物を調製した。得られたポリオレフイン榭 脂組成物を用いて、室温クロ口ホルム不溶成分量を測定した。また、射出成形機 (IS 55、東芝機械株式会社製）にて ASTM試験片を成形した。溶融混練条件および射 出成形条件は実施例 1と同じである。室温クロ口ホルム不溶成分中に含まれるブロッ ク (b)に由来する成分の含有量、 C /C 比および成形品の物性を表 9に示す。 [] [Image] 02908 4) 5 parts by weight and 30 parts by weight of polyphenylene oxide (B4-1) were melt-kneaded with a twin-screw extruder to prepare a pelleted polyolefin resin composition. The room temperature black mouth form insoluble component amount was measured using the obtained polyolefin resin composition. In addition, ASTM test pieces were molded with an injection molding machine (IS 55, manufactured by Toshiba Machine Co., Ltd.). The melt-kneading conditions and the injection molding conditions are the same as in Example 1. Table 9 shows the content of components derived from block (b) contained in the room-temperature chloroform-insoluble component, the C / C ratio, and the physical properties of the molded product.
insol sol  insol sol
[0292] [実施例 29〜36]  [Examples 29 to 36]
ポリオレフイン、ォレフィン系ブロック共重合体およびポリフエ-レンオキサイドの種 類および量、溶融混練時の混練温度および射出成形時のシリンダー温度を表 9に記 載のように変更した以外は実施例 28と同様にして ASTM試験片を成形した。ブロッ ク (b)含有量、 C /C 比および成形品の物性を表 9に示す。  The same as Example 28, except that the types and amounts of polyolefin, olefin-based block copolymer and polyphenylene oxide, the kneading temperature during melt kneading and the cylinder temperature during injection molding were changed as shown in Table 9. An ASTM test piece was molded. Table 9 shows the block (b) content, C / C ratio, and physical properties of the molded product.
insol sol  insol sol
[0293] [比較例 20〜26]  [0293] [Comparative Examples 20 to 26]
ポリオレフインおよびポリフエ-レンオキサイドの種類および量、溶融混練時の混練 温度および射出成形時のシリンダー温度を表 9に記載のように変更し、かつォレフィ ン系ブロック共重合体を使用しな力つた以外は実施例 28と同様にして ASTM試験 片を成形した。ブロック (b)含有量、 C /C 比および成形品の物性を表 9に示す。  The types and amounts of polyolefin and polyphenylene oxide, the kneading temperature during melt-kneading and the cylinder temperature during injection molding were changed as shown in Table 9, and only when an olefin-based block copolymer was used In the same manner as in Example 28, an ASTM test piece was molded. Table 9 shows the block (b) content, C / C ratio, and physical properties of the molded product.
insol sol  insol sol
[0294] [表 9] [0294] [Table 9]
表 9 Table 9
Figure imgf000092_0001
Figure imgf000092_0001
[0295] [製造例 17] [0295] [Production Example 17]
ブロックポリマーの合成  Synthesis of block polymer
製造例 9にお 、て使用したハロゲンィ匕ポリプロピレン (ポリプロピレン換算重量平均 分子量 Mw=82,800、ポリプロピレン換算数平均分子量 Mn=41, 300、臭素平均 導入本数として 1. 3本 Z鎖）を、スチレン Zメタクリル酸メチル (モル比で 7： 3)のモノ マー混合液を、ポリマー濃度が 189gZLになるようにカ卩え、窒素パブリングによる脱 酸素操作を行った。その後、臭化銅 (I)： PMDETAの 1 : 2 (mol比）のトルエン溶液 をノヽロゲンィ匕ポリプロピレンのハロゲン含有量に対し、 3. 0当量の臭ィ匕銅 (I)となるよ うに加え、加温 '攪拌した。 100°Cで 5時間重合したところで、氷浴で冷却し、ポリマー を析出させた後、濾過し、メタノールで洗浄した。得られたポリマーを減圧下（lOTorr )、 80°Cで乾燥することで白色のポリマー（以下、ブロックポリマー (A2— 15)とする） を得た。 ^H—NMRより求めたポリマーの組成分析結果を表 10にまとめた。  In Production Example 9, the halogenated polypropylene (polypropylene equivalent weight average molecular weight Mw = 82,800, polypropylene equivalent number average molecular weight Mn = 41,300, bromine average introduction number 1.3 Z chain) A monomer mixture of methyl acid (molar ratio 7: 3) was prepared so that the polymer concentration was 189 gZL, and deoxygenation was performed by nitrogen publishing. After that, add 1: 2 (mol ratio) toluene solution of copper bromide (PM): PMDETA to 3.0 equivalent of odorous copper (I) with respect to the halogen content of neurogenic polypropylene. Warm, stir. After polymerization at 100 ° C. for 5 hours, the mixture was cooled in an ice bath to precipitate a polymer, filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (lOTorr) to obtain a white polymer (hereinafter referred to as block polymer (A2-15)). Table 10 summarizes the results of polymer composition analysis determined by ^ H-NMR.
[0296] [製造例 18]  [0296] [Production Example 18]
ブロックポリマーの合成  Synthesis of block polymer
製造例 12において製造したハロゲンィ匕ポリプロピレン (ポリプロピレン換算重量平 均分子量 Mw= 106,000、ポリプロピレン換算数平均分子量 Mn= 56,400、臭素平 均導入本数として 1. 9本 Z鎖）をガラス製重合器に入れ、アクリル酸 2 ェチルへ キシル（2— EHA)とメタクリル酸グリシジル（GMA)がそれぞれ 3. 0M、 0. 30Mにな るように調製したトルエン溶液を、ポリマー濃度が 93gZLになるように加え、窒素バ プリングによる脱酸素操作を行った。その後、臭化銅 (I)： PMDETAの 1 : 2 (mol比） のトルエン溶液をノヽロゲン化ポリプロピレンのハロゲン含有量に対し、 2当量の臭化 銅 (I)となるように加え、加温 ·攪拌した。 75°Cで 1時間重合したところで、氷浴で冷却 し、ポリマーを濾過し、メタノールで洗浄した。得られたポリマーを減圧下（10Torr)、 80°Cで乾燥することで白色のポリマー（以下、ブロックポリマー (A2— 16)とする）を 得た。 ¾ - NMRより求めたポリマーの組成分析結果を表 10にまとめた。  Halogenated polypropylene produced in Production Example 12 (polypropylene equivalent weight average molecular weight Mw = 106,000, polypropylene equivalent number average molecular weight Mn = 56,400, bromine average introduction number 1.9 Z chain) was placed in a glass polymerizer, Toluene solution prepared so that hexyl acrylate (2-EHA) and glycidyl methacrylate (GMA) are 3.0 M and 0.30 M, respectively, is added so that the polymer concentration becomes 93 gZL, and nitrogen gas is added. A deoxygenation operation by pulling was performed. Then, add a 1: 2 (mol ratio) toluene solution of copper (I) bromide: PMDETA to the halogen content of the halogenated polypropylene to give 2 equivalents of copper (I) bromide. · Stir. After polymerization at 75 ° C. for 1 hour, the mixture was cooled in an ice bath, and the polymer was filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (10 Torr) to obtain a white polymer (hereinafter referred to as block polymer (A2-16)). Table 10 summarizes the results of polymer composition analysis determined by ¾-NMR.
[0297] [製造例 19] [0297] [Production Example 19]
ブロックポリマーの合成  Synthesis of block polymer
製造例 12において製造したハロゲンィ匕ポリプロピレン (ポリプロピレン換算重量平 均分子量 Mw= 106,000、ポリプロピレン換算数平均分子量 Mn= 56,400、臭素平 均導入本数として 1. 9本 Z鎖）をガラス製重合器に入れ、アクリル酸 n ブチル (n BuA)とアクリロニトリル (AN)とメタクリル酸グリシジル (GMA)がそれぞれ 2. 1M、 0 . 90M、0. 3Mになるように調製したトルエン溶液を、ポリマー濃度が 93g/Lになる ように加え、窒素パブリングによる脱酸素操作を行った。その後、臭化銅 (I)： PMDE TAの 1： 2 (mol比）のトルエン溶液をノヽロゲン化ポリプロピレンのハロゲン含有量に対 し、 2当量の臭ィ匕銅 (I)となるようにカ卩え、加温 '攪拌した。 75°Cで 6時間重合したとこ ろで、氷浴で冷却し、ポリマーを濾過し、メタノールで洗浄した。得られたポリマーを 減圧下（10Torr)、 80°Cで乾燥することで白色のポリマー（以下、ブロックポリマー（A 2- 17)とする）を得た。 ^H—NMRより求めたポリマーの組成分析結果を表 10にまと めた。 Halogenated polypropylene produced in Production Example 12 Average molecular weight Mw = 106,000, polypropylene equivalent number average molecular weight Mn = 56,400, bromine average introduction number 1.9 as Z chain) was put in a glass polymerizer and n-butyl acrylate (n BuA) and acrylonitrile (AN) Toluene solutions prepared so that glycidyl methacrylate (GMA) was 2.1 M, 0.90 M, and 0.3 M were added to a polymer concentration of 93 g / L, and deoxygenation was performed by nitrogen publishing. . After that, a 1: 2 (mol ratio) toluene solution of copper (I) bromide: PMDE TA was added to the halogen content of the halogenated polypropylene to give 2 equivalents of odorous copper (I). Barking, warming 'stirring. After polymerization at 75 ° C. for 6 hours, the mixture was cooled in an ice bath, and the polymer was filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (10 Torr) to obtain a white polymer (hereinafter referred to as block polymer (A 2-17)). Table 10 summarizes the composition analysis results of the polymer obtained from ^ H-NMR.
[0298] [製造例 20]  [0298] [Production Example 20]
ブロックポリマーの合成  Synthesis of block polymer
製造例 12において製造したハロゲンィ匕ポリプロピレン (ポリプロピレン換算重量平 均分子量 Mw= 106,000、ポリプロピレン換算数平均分子量 Mn= 56,400、臭素平 均導入本数として 1. 9本 Z鎖）をガラス製重合器に入れ、メタクリル酸グリシジル (G MA)が 3. 0Mになるように調製したトルエン溶液を、ポリマー濃度が 93gZLになる ように加え、窒素パブリングによる脱酸素操作を行った。その後、臭化銅 (I)： PMDE TAの 1： 2 (mol比）のトルエン溶液をノヽロゲン化ポリプロピレンのハロゲン含有量に対 し、 2当量の臭ィ匕銅 (I)となるようにカ卩え、加温 '攪拌した。 75°Cで 20分間重合したと ころで、氷浴で冷却し、ポリマーを濾過し、メタノールで洗浄した。得られたポリマーを 減圧下（10Torr)、 80°Cで乾燥することで白色のポリマー（以下、ブロックポリマー（A 2- 18)とする）を得た。 ^H—NMRより求めたポリマーの組成分析結果を表 10にまと めた。  Halogenated polypropylene produced in Production Example 12 (polypropylene equivalent weight average molecular weight Mw = 106,000, polypropylene equivalent number average molecular weight Mn = 56,400, bromine average introduction number 1.9 Z chain) was placed in a glass polymerizer, A toluene solution prepared so that glycidyl methacrylate (GMA) was 3.0 M was added to a polymer concentration of 93 gZL, and deoxygenation was performed by nitrogen publishing. After that, a 1: 2 (mol ratio) toluene solution of copper (I) bromide: PMDE TA was added to the halogen content of the halogenated polypropylene to give 2 equivalents of odorous copper (I). Barking, warming 'stirring. After polymerization for 20 minutes at 75 ° C, the mixture was cooled in an ice bath, the polymer was filtered, and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (10 Torr) to obtain a white polymer (hereinafter referred to as block polymer (A 2-18)). Table 10 summarizes the composition analysis results of the polymer obtained from ^ H-NMR.
[0299] [製造例 21]  [0299] [Production Example 21]
ブロックポリマーの合成  Synthesis of block polymer
ポリプロピレン (プライムポリマー社製 S 119)をガラス製反応器に入れ、ポリマー濃 度が lOOgZLになるよう、クロ口ベンゼンをカ卩えて 120°Cで 2時間加熱撹拌した。そ の後、ポリプロピレン 100重量部に対して 2. 5重量部の N—ブロモスクシンイミドをカロ えて 100°Cで 2時間溶液状態で反応を行った。反応液を 4Lのアセトン中に注ぎ、析 出したポリマーをろ過した。ポリマーを再度アセトンに入れ 10分間攪拌することで固 液洗浄した後に再度濾取し、 80°C、 lOTorrの減圧条件下で 10時間乾燥させた。得 られたポリマー中に含まれる臭素原子の含有量は、イオンクロマトグラフィー分析から 0. 55wt%であった。また、該ポリマーの分子量を GPC (ポリプロピレン換算）により 測定したところ、 Mw= 101,000、 Mn=43,000、 Mw/Mn= 2. 35であり、 DSC の測定結果より融点が 153°Cであった。このハロゲンィ匕ポリプロピレンをガラス製重合 器に入れ、アクリル酸— n—ブチル（nBA)とメタクリル酸グリシジル（GMA)がそれぞ れ 3. 0M、0. 30Mになるように調製したトルエン溶液を、ポリマー濃度が 93g/Lに なるように加え、窒素パブリングによる脱酸素操作を行った。その後、臭化銅 (I)： PM DETAの 1： 2 (mol比）のトルエン溶液をハロゲン化ポリプロピレンのハロゲン含有量 に対し、 2当量の臭ィ匕銅 (I)となるように加え、加温'攪拌した。 75°Cで 1時間重合し たところで、氷浴で冷却し、ポリマーを濾過し、メタノールで洗浄した。得られたポリマ 一を減圧下（lOTorr)、 80°Cで乾燥することで白色のポリマー（以下、ブロックポリマ 一 (A2- 19)とする）を得た。 NMRより求めたポリマーの組成分析結果を表 10 にまとめた。 Polypropylene (Prime Polymer S 119) was placed in a glass reactor, and the mixture was stirred and heated at 120 ° C. for 2 hours with the black benzene added so that the polymer concentration became lOOgZL. So Thereafter, 2.5 parts by weight of N-bromosuccinimide was added to 100 parts by weight of polypropylene and reacted in a solution state at 100 ° C. for 2 hours. The reaction solution was poured into 4 L of acetone, and the precipitated polymer was filtered. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then collected again by filtration and dried under reduced pressure conditions of 80 ° C. and lOTorr for 10 hours. The content of bromine atoms contained in the obtained polymer was 0.55 wt% from ion chromatography analysis. Further, when the molecular weight of the polymer was measured by GPC (polypropylene conversion), it was Mw = 101,000, Mn = 43,000, Mw / Mn = 2.35, and the melting point was 153 ° C. from the DSC measurement result. This halogenated polypropylene is put into a glass polymerizer, and a toluene solution prepared so that acrylic acid-n-butyl (nBA) and glycidyl methacrylate (GMA) are 3.0 M and 0.30 M, respectively. In addition to the concentration of 93 g / L, deoxygenation was performed by nitrogen publishing. After that, add a 1: 2 (mol ratio) toluene solution of copper bromide (I): PM DETA to the halogen content of the halogenated polypropylene to give 2 equivalents of odorous copper (I). Warm 'stirring. After polymerization at 75 ° C. for 1 hour, the mixture was cooled in an ice bath, and the polymer was filtered and washed with methanol. The obtained polymer was dried at 80 ° C. under reduced pressure (lOTorr) to obtain a white polymer (hereinafter referred to as block polymer (A2-19)). Table 10 summarizes the results of the polymer composition analysis determined by NMR.
[比較製造例 1]  [Comparative Production Example 1]
ブロックポリマーの合成 Synthesis of block polymer
株式会社プライムポリマー社製該ホモポリプロピレン F 102W (MFR = 2gZ 10分 、引張弾性率 l,600MPa、引張破壊呼びひずみ 130%である。） 100重量に、無水 マレイン酸 (和光純薬社製。以下、「MAH」と略記することがある。） 1重量部、ターシ ャリーブチルパーォキシベンゾエイト（日本油脂社製、商品名パーブチル Z) 0. 5重 量部をアセトンに溶解させた溶液をドライブレンドした。その後、二軸混練機（日本製 鋼所製、 TEX— 30)を用いて榭脂温度 230°C、スクリュ—回転数 200rpm、吐出量 1 00gZ分にて押し出し、マレイン酸変性ポリプロピレン（以下、変性ポリマー（P— 1)と する）を得た。得られた MAH— PPをキシレンに溶解、アセトンに再沈させて精製し、 無水マレイン酸のグラフト量を測定したところ 0. 75重量％であり、 MFRは 400gZlO 分であった。 Homopolypropylene F 102W manufactured by Prime Polymer Co., Ltd. (MFR = 2gZ 10 minutes, tensile elastic modulus l, 600 MPa, tensile fracture nominal strain 130%) Maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., below) 1 part by weight, tertiary butyl peroxybenzoate (Nippon Yushi Co., Ltd., trade name: Perbutyl Z) A solution of 0.5 part by weight dissolved in acetone. Dry blended. Then, using a twin-screw kneader (manufactured by Nippon Steel Co., Ltd., TEX-30), it was extruded at a resin temperature of 230 ° C, a screw rotation speed of 200 rpm, and a discharge rate of 100 gZ. A polymer (referred to as P-1) was obtained. The obtained MAH-PP was dissolved in xylene, purified by reprecipitation in acetone, and the grafting amount of maleic anhydride was measured to be 0.75% by weight, and the MFR was 400gZlO. Minutes.
[製造例 22]  [Production Example 22]
ブロックポリマーの合成 Synthesis of block polymer
充分に窒素置換した内容積 500mLのガラス製反応器に、上記製造例 8で得たノヽ ロゲン化ポリプロピレン 15gとアクリル酸ブチル（nBuA) 25. 2ml、メタクリル酸グリシ ジル（GMA) IO. 3ml、トルエン 217mLを入れ、 25°Cで溶液を窒素置換（30LZhr , 0. 5時間）した。このスラリーに、臭化銅（I) 73mg、 PMDETA 0. 21mlを加え、 8 0°Cで 4時間重合を行った。反応液をろ過し、フィルター上の固体をメタノールで洗浄 後ポリマーを減圧乾燥して 19. 9gの固体状ポリマーを得た (以下、ブロックポリマー（ A2— 20)とする）。得られたポリマー 3. OOgを取り、アセトン 150mlを用いてソクスレ 一抽出を還流下 9時間行った。抽出残を減圧乾燥して 2. 98gのポリマーを得た。 ¾ —NMRより求めたポリマーの組成分析結果を表 10にまとめた。  Into a glass reactor with an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of the non-propylated polypropylene obtained in Production Example 8 above, 25.2 ml of butyl acrylate (nBuA), 3 ml of glycidyl methacrylate (GMA) IO., Toluene 217 mL was added, and the solution was purged with nitrogen at 25 ° C. (30 LZhr, 0.5 hour). To this slurry, 73 mg of copper (I) bromide and 0.21 ml of PMDETA were added, and polymerization was carried out at 80 ° C. for 4 hours. The reaction solution was filtered, the solid on the filter was washed with methanol, and the polymer was dried under reduced pressure to obtain 19.9 g of a solid polymer (hereinafter referred to as block polymer (A2-20)). 3. OOg of the obtained polymer was taken, and Soxle extraction was performed using 150 ml of acetone for 9 hours under reflux. The extraction residue was dried under reduced pressure to obtain 2.98 g of polymer. Table 10 summarizes the results of polymer composition analysis determined by NMR.
[製造例 23] [Production Example 23]
ブロックポリマーの合成 Synthesis of block polymer
アクリル酸ブチル（nBuA)、メタクリル酸グリシジル（GMA)、トルエンの仕込み量を それぞれ、 5. 2ml/l l. 6mlZ236mlとする以外は、製造例 22と同様な手法で重 合を行い、 16. 9gのポリマー（以下、ブロックポリマー（A2— 21)とする）を得た。 —NMR分析より、 PPZP(nBuA- Co- GMA)の組成比（重量比）は、 88/12 (wt%) であった。  Polymerization was conducted in the same manner as in Production Example 22 except that the amounts of butyl acrylate (nBuA), glycidyl methacrylate (GMA), and toluene were changed to 5.2 ml / l l. (Hereinafter referred to as block polymer (A2-21)). From the NMR analysis, the composition ratio (weight ratio) of PPZP (nBuA-Co-GMA) was 88/12 (wt%).
[製造例 24] [Production Example 24]
ブロックポリマーの合成 Synthesis of block polymer
仕込みモノマーをメタクリル酸メチル（MMA) 9. lml、メタクリル酸グリシジル（GM A) 5. 0mlとし、トルエンの仕込み量を 239mlとし、重合時間を 3. 5時間する以外は 、製造例 22と同様な手法で重合を行い、 17. 3gのポリマー（以下、ブロックポリマー（ A2- 22)とする）を得た。 ^H—NMRより求めたポリマーの組成分析結果を表 10にま とめた。  The same as in Production Example 22 except that the charged monomer was 9.1 ml of methyl methacrylate (MMA), 5.0 ml of glycidyl methacrylate (GMA), the charged amount of toluene was 239 ml, and the polymerization time was 3.5 hours. Polymerization was performed by a method to obtain 17.3 g of a polymer (hereinafter referred to as a block polymer (A2-22)). Table 10 summarizes the composition analysis results of the polymer determined by ^ H-NMR.
[製造例 25] [Production Example 25]
ブロックポリマーの合成 仕込みモノマーをスチレン（St) 20. 3ml、メタクリル酸グリシジル（GMA) 10. 3ml とし、トルエンの仕込み量を 222mlとし、重合時間を 3. 5時間とする以外は、製造例 22と同様な手法で重合を行い、 16. lgのポリマー（以下、ブロックポリマー（A2— 23 )とする）を得た。 iH—NMRより求めたポリマーの組成分析結果を表 10にまとめた。 Synthesis of block polymer The procedure was the same as in Production Example 22, except that the monomer used was 20.3 ml of styrene (St), 10.3 ml of glycidyl methacrylate (GMA), the amount of toluene was 222 ml, and the polymerization time was 3.5 hours. Polymerization was performed to obtain 16. lg of polymer (hereinafter referred to as block polymer (A2-23)). Table 10 summarizes the composition analysis results of the polymers obtained from iH-NMR.
[製造例 26] [Production Example 26]
ハロゲン化ポリプロピレンの合成 Synthesis of halogenated polypropylene
特開 2002— 145944号公報の実施例に記載の方法に準じて製造したプロピレン Z10—ゥンデセン 1 オール共重合ポリマー（ポリプロピレン換算重量平均分子 量 Mw= 149,000、ポリプロピレン換算数平均分子量 Mn= 66, 180、融点： 153. 8 °C、水酸基含量: 0. 117mmolZg)を、ガラス製反応器に入れ、ポリマー濃度が 100 gZLになるよう、へキサンを加えスラリー状態にした。ポリマーに存在する水酸基の 量に対し、 5倍当量の 2 ブロモイソ酪酸プロミド添加し、 60°Cに昇温し、 3時間加熱 撹拌した。反応液を、 20°CZhの冷却速度で 20°Cまで冷却し、ポリマーを濾別した。 ポリマーを、再度アセトンに入れ 10分間攪拌することで固液洗浄した後に再度濾取 した。得られた白色ポリマーを 50°C、 lOTorrの減圧条件下で 10時間乾燥させた。 D SCの測定結果より融点が 153. 1°Cであり、 NMR分析より、 2 ブロモイソ酪酸 プロミド由来の臭素が導入された末端が平均導入本数として 7. 5本 Z鎖であった。 1 H—NMRより求めたポリマーの組成分析結果を表 10にまとめた。 Propylene Z10-undecene 1-ol copolymer produced according to the method described in the examples of JP-A-2002-145944 (polypropylene equivalent weight average molecular weight Mw = 149,000, polypropylene equivalent number average molecular weight Mn = 66, 180, Melting point: 153.8 ° C., hydroxyl group content: 0.117 mmol Zg) was placed in a glass reactor, and hexane was added to form a slurry so that the polymer concentration was 100 gZL. To the amount of hydroxyl groups present in the polymer, 5-fold equivalent of 2-bromoisobutyric acid promide was added, the temperature was raised to 60 ° C, and the mixture was heated and stirred for 3 hours. The reaction solution was cooled to 20 ° C. at a cooling rate of 20 ° C. Zh, and the polymer was filtered off. The polymer was again placed in acetone and stirred for 10 minutes for solid-liquid washing, and then filtered again. The obtained white polymer was dried for 10 hours under reduced pressure at 50 ° C. and lOTorr. From the DSC measurement result, the melting point was 153.1 ° C, and from NMR analysis, the terminal introduced with bromine derived from 2-bromoisobutyric acid promide was an average of 7.5 Z-chains. Table 10 summarizes the results of polymer composition analysis determined by 1 H-NMR.
[製造例 27] [Production Example 27]
ブロックポリマーの合成 Synthesis of block polymer
充分に窒素置換した内容積 500mLのガラス製反応器に、上記製造例 26で得たノヽ ロゲン化ポリプロピレン 15gとアクリル酸ブチル（nBuA) 12. lml、メタクリル酸グリシ ジル（GMA) 5. 0ml、トルエン 236mLを入れ、 25°Cで溶液を窒素置換（30LZhr, 0. 5時間）した。このスラリーに、臭化銅（I) 73mg、 PMDETA 0. 21mlをカ卩え、 80 °Cで 4時間重合を行った。反応液をろ過し、フィルター上の固体をメタノールで洗浄 後ポリマーを減圧乾燥して 19. 0gの固体状ポリマーを得た (以下、ブロックポリマー（ A2— 24)とする）。得られたポリマー 3. 00gを取り、アセトン 150mlを用いてソクスレ 一抽出を還流下 9時間行った。抽出残を減圧乾燥して 2. 94gのポリマーを得た。 ¾ — NMRより求めたポリマーの組成分析結果を表 10にまとめた。 Into a glass reactor with an internal volume of 500 mL sufficiently purged with nitrogen, 15 g of the non-propylated polypropylene obtained in Production Example 26 above, 12. lml of butyl acrylate (nBuA), 5.0 ml of glycidyl methacrylate (GMA), toluene 236 mL was added, and the solution was purged with nitrogen at 25 ° C. (30 LZhr, 0.5 hour). To this slurry, 73 mg of copper (I) bromide and 0.21 ml of PMDETA were added, and polymerization was carried out at 80 ° C. for 4 hours. The reaction solution was filtered, the solid on the filter was washed with methanol, and the polymer was dried under reduced pressure to obtain 19.0 g of a solid polymer (hereinafter referred to as block polymer (A2-24)). 3.00 g of the obtained polymer was taken, and Soxle extraction was performed using 150 ml of acetone for 9 hours under reflux. The extraction residue was dried under reduced pressure to obtain 2.94 g of polymer. ¾ — Table 10 summarizes the results of NMR polymer composition analysis.
[製造例 28]  [Production Example 28]
ブロックポリマーの合成  Synthesis of block polymer
充分に窒素置換した内容積 500mLのガラス製反応器に、上記製造例 8で得たノヽ ロゲン化ポリプロピレン 30gとスチレン（St) 1. 4ml、マレイン酸無水物（MAH) l. 2g 、トルエン 265mLを入れ、 25°Cで溶液を窒素置換（30LZhr, 0. 5時間）した。この スラリーに、シクロペンタジェ-ルカルボ-ル鉄（II) 2量体 143mgをカ卩え、 80°Cで 4 時間重合を行った。反応液をろ過し、フィルター上の固体をメタノールで洗浄後ポリ マーを減圧乾燥して 31. 9gの固体状ポリマーを得た（以下、ブロックポリマー (A2— 26)とする）。得られたポリマー 3. 00gを取り、アセトン 150mlを用いてソクスレー抽出 を還流下 9時間行った。抽出残を減圧乾燥して 2. 97gのポリマーを得た。 'Η-ΝΜ Rより求めたポリマーの組成分析結果を表 10にまとめた。  Into a glass reactor with an internal volume of 500 mL that has been sufficiently purged with nitrogen, 30 g of the non-propylated polypropylene obtained in Production Example 8 above, 1.4 ml of styrene (St), 1 g of maleic anhydride (MAH), and 265 mL of toluene are added. The solution was purged with nitrogen at 25 ° C. (30 LZhr, 0.5 hour). To this slurry, 143 mg of cyclopentagel carboiron (II) dimer was added and polymerized at 80 ° C. for 4 hours. The reaction solution was filtered, and the solid on the filter was washed with methanol, and then the polymer was dried under reduced pressure to obtain 31.9 g of a solid polymer (hereinafter referred to as block polymer (A2-26)). 3.00 g of the obtained polymer was taken, and Soxhlet extraction was performed using 150 ml of acetone for 9 hours under reflux. The extraction residue was dried under reduced pressure to obtain 2.97 g of polymer. Table 10 summarizes the results of polymer composition analysis obtained from 'Η-ΝΜ R.
[製造例 29]  [Production Example 29]
ブロックポリマーの合成  Synthesis of block polymer
以下の実施例で使用したエポキシスチレン (m,p混合物）は、 Polymer 40(9), 2411 (1 999)記載の方法で合成した。  The epoxy styrene (m, p mixture) used in the following examples was synthesized by the method described in Polymer 40 (9), 2411 (1 999).
[0302] 上記製造例 8で得たハロゲン化ポリプロピレン 60. OgZL、アクリル酸 nブチル 495 ml/ エポキシスチレン（m, p—混合物） 210mlZL、アセトン 295mlZLの濃度 でコンデンサー付き 4つ口フラスコに仕込み、 30分間窒素パブリングさせたのち、別 途調整した 0. 8molZLの PMDETAと臭化第一銅のトルエン調整液を 25mlZLの 濃度になるよう添加して、 55°Cで 8時間反応させた。反応液をろ取して得られた固体 をアセトンで数回洗浄し、 60°Cで減圧乾燥して、 目的のエポキシ基含有ブロックポリ マー（以下、ブロックポリマー (A2— 25)とする）を得た。得られたブロックポリマーの1 H—NMRより求めたポリマーの組成分析結果を表 10にまとめた。 [0302] Halogenated polypropylene obtained in Production Example 8 60. OgZL, n-butyl acrylate 495 ml / epoxystyrene (m, p-mixture) 210mlZL, acetone 295mlZL Concentrate in a 4-necked flask with condenser, 30 After nitrogen publishing for minutes, 0.8 mol ZL of PMDETA and cuprous bromide prepared in toluene were added to a concentration of 25 ml ZL and reacted at 55 ° C for 8 hours. The solid obtained by filtering the reaction solution was washed several times with acetone and dried under reduced pressure at 60 ° C to obtain the target epoxy group-containing block polymer (hereinafter referred to as block polymer (A2-25)). Obtained. Table 10 summarizes the composition analysis results of the polymer obtained from 1 H-NMR of the obtained block polymer.
[0303] [表 10] 表 1 [0303] [Table 10] table 1
Figure imgf000099_0001
Figure imgf000099_0001
[実施例 37] [Example 37]
[0304] [ 1]ポリオレフイン (Al— 5) 50重量部、ポリオレフイン (A1— 4) 30重量部、および 前記製造例 9で得られたブロックポリマー (A2— 7) 20重量部を予備混合し、株式会 社テクノベル製二軸押出機 KZW— 15Gダイ径 15πιπι φ、 LZD= 30二軸押出機を 用いて 200°Cの温度で溶融混練した後ストランド状の押出し、切断してペレットを製 造した。このペレットを 80°Cの減圧乾燥機でー晚加熱して、ポリオレフイン (A1— 4)と ポリオレフイン (A1 - 5)との重合体組成物を得た。  [0304] [1] Polyolefin (Al-5) 50 parts by weight, polyolefin (A1-4) 30 parts by weight, and 20 parts by weight of the block polymer (A2-7) obtained in Production Example 9 were premixed, Technobel's twin screw extruder KZW-15G die diameter 15πιπι φ, LZD = 30 Using a twin screw extruder, melt-kneaded at a temperature of 200 ° C, extruded into strands, cut to produce pellets . This pellet was heated in a vacuum dryer at 80 ° C. to obtain a polymer composition of polyolefin (A1-4) and polyolefin (A1-5).
[0305] [2]三台の押出機を 1つのダイに結合した押出成形装置を用いて、それぞれの押 出機に株式会社プライムポリマー製ランダムポリプロピレン (グレード F227D ; MFR = 7. OgZlO分、引張弾性率 950MPa、引張破壊呼びひずみ 200%以上）、上記の [ 1]で得た重合体組成物、および三井ィ匕学株式会社製ポリエチレンテレフタレート（ グレード J135)を供給し、押し出し時の最高温度をランダムポリプロピレンが 220°C、 重合体組成物が 230°C、ポリエチレンテレフタレートが 280°Cになるように設定して、 押出成形装置の Tダイ（ダイ径は 40mm φ )から、ランダムポリプロピレン（40 μ χη) / 重合体組成物（40 μ m) Zポリエチレンテレフタレート（160 μ m)の順に積層した三 層構造になるようにして共押出成形を行って、（L1)層がランダムポリプロピレン層、（ L2)層がブロックポリマーを含む層、（L3)層がポリエチレンテレフタレートである三層 からなる積層構造体を製造した。  [0305] [2] Using an extrusion molding machine that combined three extruders into one die, each extruder was supplied with Prime Polymer random polypropylene (grade F227D; MFR = 7. OgZlO min, tensile Supply elastic modulus 950MPa, nominal tensile fracture strain 200% or more), polymer composition obtained in [1] above, and polyethylene terephthalate (grade J135) manufactured by Mitsui Engineering Co., Ltd. Random polypropylene is set to 220 ° C, polymer composition is set to 230 ° C, and polyethylene terephthalate is set to 280 ° C. From the T die of the extrusion molding machine (die diameter is 40mm φ), random polypropylene (40 μm χη) / polymer composition (40 μm) Z polyethylene terephthalate (160 μm) laminated in order to form a three-layer structure, and (L1) layer is a random polypropylene layer, (L2 ) There layer containing the block polymer, to produce a layered structure consisting of three layers is polyethylene terephthalate (L3) layer.
上記 [2]で得られた積層構造体にっ 、て、（L2)層と (L3)層との界面接着強度を、 剥離雰囲気温度 23°C、剥離速度 500mmZ分、ピール幅 10mmの条件で T型剥離 して求めた。その結果を表 11に示した。また、はく離の際の形態を表 11に示した。  With the laminated structure obtained in [2] above, the interfacial adhesive strength between the (L2) layer and the (L3) layer was determined under the conditions of a peeling atmosphere temperature of 23 ° C, a peeling speed of 500 mmZ, and a peel width of 10 mm. Obtained by peeling T-type. The results are shown in Table 11. Table 11 shows the mode of peeling.
[0306] 榭脂切れとは (L3)層が破壊して剥離したことを示し、凝集剥離とは (L2)層が破壊 して剥離したことを示し、剥離面荒とは剥離の際に (L3)層に (L2)層が残って剥離し たことを示し、良好とは剥離の際に (L3)層に (L2)層が残らず、接着強度を発現せ ずに剥離したことを示し、接着不可とは剥離試験を行う前に試料調整段階で剥離し てしまったことを示す。 [0306] The loss of grease means that the (L3) layer was broken and peeled off, and the cohesive peeling means that the (L2) layer was broken and peeled. The (L2) layer remained in the (L3) layer and peeled, and `` good '' means that the (L2) layer did not remain in the (L3) layer during peeling, and it peeled without exhibiting adhesive strength. “No adhesion” means that the sample was peeled off at the sample preparation stage before the peel test.
[実施例 38〜51]  [Examples 38 to 51]
[0307] 実施例 37において、表 11に示した条件に変更した以外は実施例 37と同様にして T型剥離試験を行った。結果を表 11に示した。 [0307] In Example 37, the conditions were changed to those shown in Table 11 except that the conditions were changed as shown in Table 11. A T-type peel test was performed. The results are shown in Table 11.
[実施例 52]  [Example 52]
[0308] [1]ポリオレフイン (A1— 5) 68重量部、ポリオレフイン (A1— 4) 23重量部、および 前記製造例 28で得られたブロックポリマー (Α2— 25) 9重量部を予備混合し、株式 会社テクノベル製二軸押出機 KZW— 15Gダイ径 15πιπι φ、 LZD= 30二軸押出機 を用いて 200°Cの温度で溶融混練した後ストランド状の押出し、切断してペレットを 製造した。このペレットを 80°Cの減圧乾燥機で一晩加熱して、ポリオレフイン (A1— 4 )とポリオレフイン (A1 - 5)との重合体組成物を得た。  [0308] [1] 68 parts by weight of polyolefin (A1-5), 23 parts by weight of polyolefin (A1-4), and 9 parts by weight of the block polymer (Α2-25) obtained in Production Example 28 were premixed, A twin-screw extruder KZW-15G die diameter 15πιπιφ, LZD = 30 twin-screw extruder manufactured by Technobel Co., Ltd. was melt-kneaded at a temperature of 200 ° C., and then extruded into strands to produce pellets. The pellets were heated overnight in a vacuum dryer at 80 ° C. to obtain a polymer composition of polyolefin (A1-4) and polyolefin (A1-5).
[0309] [2]三台の押出機を 1つのダイに結合した押出成形装置を用いて、それぞれの押 出機に株式会社プライムポリマー製ランダムポリプロピレン (グレード F227D ;MFR = 7. OgZlO分、引張弾性率 950MPa、引張破壊呼びひずみ 200%以上）、上記の [ 1 ]で得た重合体組成物、および株式会社クラレ製エチレン ·ビュルアルコ一ル共重 合体 (商品名工バール、グレード L101A)を供給し、押し出し時の最高温度をランダム ポリプロピレンが 220°C、重合体組成物が 230°C、エチレン 'ビュルアルコール共重 合体が 220°Cになるように設定して、押出成形装置の Tダイ (ダイ径は 40mm φ )から 、ランダムポリプロピレン（40 μ m) Z重合体組成物（40 μ m) Zエチレン ·ビュルアル コール共重合体（ 160 m)の順に積層した三層構造になるようにして共押出成形を 行って、（L1)層がランダムポリプロピレン層、（L2)層がブロックポリマーを含む層、（ L3)層がエチレン 'ビュルアルコール共重合体である三層力 なる積層構造体を製 し 7こ。  [0309] [2] Using an extrusion molding machine that combined three extruders into one die, each extruder was supplied with Prime Polymer Random Polypropylene Co., Ltd. (grade F227D; MFR = 7. OgZlO, tensile And supply the polymer composition obtained in [1] above, and Kuraray Co., Ltd. ethylene-bular alcohol copolymer (trade name: Kobar, grade L101A). The maximum temperature during extrusion is set to random at 220 ° C for polypropylene, 230 ° C for the polymer composition, and 220 ° C for the ethylene butyl alcohol copolymer. Co-extrusion from a diameter of 40mmφ) to a three-layer structure in which a random polypropylene (40 μm) Z polymer composition (40 μm) Z ethylene-bulal alcohol copolymer (160 m) is laminated in this order. Form (L1) layer Random polypropylene layer, (L2) layer a layer containing a block polymer, manufactured by 7 this three layer strength becomes layered structure is (L3) layer is ethylene 'Bulle alcohol copolymer.
[0310] 上記 [2]で得られた積層構造体について、（L2)層と (L3)層との界面接着強度を、 剥離雰囲気温度 23°C、剥離速度 500mmZ分、ピール幅 10mmの条件で T型剥離 して求めた。その結果を表 11に示した。また、はく離の際の形態を表 11に示した。  [0310] For the laminated structure obtained in [2] above, the interfacial adhesion strength between the (L2) layer and the (L3) layer was determined under the conditions of a peeling atmosphere temperature of 23 ° C, a peeling speed of 500 mmZ, and a peel width of 10 mm. Obtained by peeling T-type. The results are shown in Table 11. Table 11 shows the mode of peeling.
[実施例 53]  [Example 53]
[0311] [1]ポリオレフイン (A1— 5) 68重量部、ポリオレフイン (A1— 4) 23重量部、および 前記製造例 9で得られたブロックポリマー (A2— 21) 9重量部を予備混合し、株式会 社テクノベル製二軸押出機 KZW— 15Gダイ径 15πιπι φ、 LZD= 30二軸押出機を 用いて 200°Cの温度で溶融混練した後ストランド状の押出し、切断してペレットを製 造した。このペレットを 80°Cの減圧乾燥機でー晚加熱して、ポリオレフイン (A1— 4)と ポリオレフイン (A1 - 5)との重合体組成物を得た。 [0311] [1] Polyolefin (A1-5) 68 parts by weight, polyolefin (A1-4) 23 parts by weight, and 9 parts by weight of the block polymer (A2-21) obtained in Production Example 9 were premixed, Technobel's twin screw extruder KZW—15G die diameter 15πιπι φ, LZD = 30 Using a twin screw extruder, melt-kneaded at a temperature of 200 ° C, then extruded into strands, cut into pellets Made. This pellet was heated in a vacuum dryer at 80 ° C. to obtain a polymer composition of polyolefin (A1-4) and polyolefin (A1-5).
[0312] [2]株式会社プライムポリマー製ランダムポリプロピレン（グレード F227D ;MFR= 7. OgZlO分、引張弾性率 950MPa、引張破壊呼びひずみ 200%以上）、上記の [ 1]で得た重合体組成物をそれぞれ温度 200°C、圧力 100kg · cm2でプレス成形し、 その後 20°Cに設定したプレス成形機にて急冷することにより、厚さ 100 m、長さ 80 mm、幅 10mmの大きさのプレスシートを得た。得られたプレスシートを用いて、（L1) 層がランダムポリプロピレン層、（L2)層がブロックポリマーを含む層、（L3)層が厚さ 1 00 μ mのアルミシートとして、 220°Cに設定したヒートシール試験機にて 10s間ヒート シールを行い、三層からなる積層構造体を製造した。 [0312] [2] Prime polymer random polypropylene (grade F227D; MFR = 7. OgZlO content, tensile elastic modulus 950 MPa, tensile fracture nominal strain 200% or more), polymer composition obtained in [1] above Each of these was press-molded at a temperature of 200 ° C and a pressure of 100 kg · cm 2 and then quenched with a press molding machine set at 20 ° C, resulting in a size of 100 m in thickness, 80 mm in length and 10 mm in width A press sheet was obtained. Using the obtained press sheet, set (L1) layer as random polypropylene layer, (L2) layer containing block polymer, and (L3) layer as aluminum sheet with a thickness of 100 μm, set at 220 ° C A heat seal tester was used to heat seal for 10 seconds to produce a laminated structure consisting of three layers.
[0313] 上記 [2]で得られた積層構造体について、（L2)層と (L3)層との界面接着強度を、 剥離雰囲気温度 23°C、剥離速度 500mmZ分、ピール幅 10mmの条件で T型剥離 して求めた。その結果を表 11に示した。また、はく離の際の形態を表 11に示した。  [0313] For the laminated structure obtained in [2] above, the interfacial adhesive strength between the (L2) layer and the (L3) layer was determined under the conditions of a peeling atmosphere temperature of 23 ° C, a peeling speed of 500 mmZ, and a peel width of 10 mm. Obtained by peeling T-type. The results are shown in Table 11. Table 11 shows the mode of peeling.
[実施例 54]  [Example 54]
[0314] ブロックポリマー (A2)として前記製造例 25で得られたブロックポリマー (A2— 23) を使用した以外は実施例 52と同様な方法で (L3)層としてアルミシートを含む三層か らなる積層構造体を製造した。得られた積層構造体について、（L2)層と (L3)層との 界面接着強度を、剥離雰囲気温度 23°C、剥離速度 500mmZ分、ピール幅 10mm の条件で T型剥離して求めた。その結果を表 11に示した。また、はく離の際の形態を 表 11に示した。  [0314] From the three layers containing an aluminum sheet as the (L3) layer in the same manner as in Example 52 except that the block polymer (A2-23) obtained in Production Example 25 was used as the block polymer (A2). A laminated structure was manufactured. The interfacial adhesive strength between the (L2) layer and the (L3) layer of the obtained laminated structure was determined by T-type peeling under the conditions of a peeling atmosphere temperature of 23 ° C, a peeling speed of 500 mmZ, and a peel width of 10 mm. The results are shown in Table 11. Table 11 shows the mode of peeling.
[0315] [比較例 27〜28]  [0315] [Comparative Examples 27-28]
実施例 37において、表 11に示した条件に変更した以外は実施例 37と同様にして T型剥離試験を行った。結果を表 11に示した。  In Example 37, a T-type peel test was performed in the same manner as in Example 37 except that the conditions shown in Table 11 were changed. The results are shown in Table 11.
[0316] [表 11] 表 1 1 [0316] [Table 11] Table 1 1
Figure imgf000103_0001
Figure imgf000103_0001
ポリオレフイン A1- 5 株式会社プライムポリマー製ホモポリプロピレン、 グレード J106G ( FR=15,  Polyolefin A1-5 Homopolypropylene made by Prime Polymer Co., Ltd., Grade J106G (FR = 15,
引張弹性率 1,500MPa、 引張破壊呼びひずみ 100%)  (Tensile toughness 1,500 MPa, Nominal strain at tensile fracture 100%)
ポリオレフイン A1-4 三井化学株式会社製ェチレンブテンランダムポリマ一、  Polyolefin A1-4 Ethylene butene random polymer manufactured by Mitsui Chemicals, Inc.
グレードタフマー A0550 訓=1.0、 密度 860kg/m3) Grade Tuffmer A0550 Lesson = 1.0, density 860kg / m 3 )

Claims

請求の範囲 The scope of the claims
[1] ポリオレフイン（A1)と、  [1] Polyolefin (A1),
ォレフィン系ブロックポリマー（A2)とを含んでなる榭脂組成物であって、 前記ォレフィン系ブロックポリマー（A2)力 ポリオレフイン成分であるブロック（a)と、 溶解度パラメータが 18〜25j/mの範囲にあるビュルモノマーの重合体残基である ブロック (b)を構成単位とし、前記ブロック (a)とブロック (b)とが互いに共有結合で結 ばれて ヽることを特徴とする榭脂組成物 (C)。  A resin composition comprising an olefin-based block polymer (A2), wherein the olefin-based block polymer (A2) force is a polyolefin component, and the solubility parameter is in the range of 18 to 25 j / m. A resin composition characterized in that block (b), which is a polymer residue of a certain bull monomer, is a structural unit, and block (a) and block (b) are covalently bonded to each other ( C).
[2] ポリオレフイン（Al) l〜98. 9重量0 /0と、 And [2] polyolefin (Al) l~98. 9 wt 0/0,
ォレフィン系ブロックポリマー（A2) 0. 1〜50重量0 /0と、 And Orefin based block polymer (A2) 0. 1 to 50 weight 0/0,
ポリカーボネート榭脂 (bl)、アクリル系榭脂 (b2)、ビニル重合体 (b3)およびポリフ ェ-レンオキサイド (b4)力 選ばれる 1種以上の榭脂（B) l〜98. 9重量％ (但し、 ( Al)、 （A2)および (B)の合計量を 100重量％とする。）とからなることを特徴とする請 求項 1に記載の榭脂組成物 (C)。  Polycarbonate resin (bl), Acrylic resin (b2), Vinyl polymer (b3) and Polyethylene oxide (b4) Force One or more selected resin (B) l ～ 98.9 wt% ( Wherein the total amount of (Al), (A2) and (B) is 100% by weight.)
[3] 前記ォレフィン系ブロックポリマー (A2)を構成するブロック (b)の該 (A2)中の含量 が 0. 1〜70重量％であることを特徴とする請求項 1または 2に記載の榭脂組成物（C[3] The container according to claim 1 or 2, wherein the content of the block (b) constituting the olefin-based block polymer (A2) in the (A2) is 0.1 to 70% by weight. Fat composition (C
) o ) o
[4] 前記ォレフィン系ブロックポリマー (A2)を構成するブロック (b)が、  [4] The block (b) constituting the olefin-based block polymer (A2)
(メタ)アクリル酸およびその誘導体、（メタ)アクリロニトリル、スチレンおよびその誘導 体、（メタ）アクリルアミドおよびその誘導体、マレイン酸およびその誘導体、マレイミド およびその誘導体、およびビュルエステル類力 選ばれるビュルモノマー力 誘導さ れる構成単位 1種以上の連鎖よりなることを特徴とする請求項 1〜3のいずれかに記 載の榭脂組成物 (C)。  (Meth) acrylic acid and its derivatives, (meth) acrylonitrile, styrene and its derivatives, (meth) acrylamide and its derivatives, maleic acid and its derivatives, maleimide and its derivatives, and butyl esters The resin composition (C) according to any one of claims 1 to 3, which comprises one or more types of structural units.
[5] 前記ォレフィン系ブロックポリマー (A2)を構成するブロック (b)が、  [5] The block (b) constituting the olefin-based block polymer (A2)
スチレン、アクリロニトリル、 2—ヒドロキシェチルメタタリレート、グリシジルメタタリレート およびメチルメタタリレートから選ばれる 1種以上のビュルモノマーをラジカル（共)重 合して得られる重合体の残基であることを特徴とする請求項 1〜3のいずれかに記載 の榭脂組成物 (C)。  It must be a polymer residue obtained by radical (co) polymerization of one or more butyl monomers selected from styrene, acrylonitrile, 2-hydroxyethyl methacrylate, glycidyl methacrylate and methyl methacrylate. The rosin composition (C) according to any one of claims 1 to 3, wherein:
[6] 前記ォレフィン系ブロックポリマー (A2)を構成するブロック (b)は、数平均分子量が 2,000〜200,000の範囲にあることを特徴とする請求項 1〜5のいずれかに記載の 榭脂組成物 (C)。 [6] The block (b) constituting the olefin-based block polymer (A2) has a number average molecular weight. The coffin composition (C) according to any one of claims 1 to 5, wherein the composition is in the range of 2,000 to 200,000.
[7] 前記ォレフィン系ブロックポリマー (A2)を構成するブロック（a)が、  [7] The block (a) constituting the olefin-based block polymer (A2)
70°C以上の融点を有する結晶性ポリオレフイン残基であることを特徴とする請求項 1 2. A crystalline polyolefin residue having a melting point of 70 ° C. or higher.
〜5の 、ずれかに記載の榭脂組成物（C)。 The resin composition (C) according to any one of 5 to 5.
[8] 榭脂組成物の室温クロ口ホルム不溶成分中のブロック (b)に由来する成分の含有 量が 0. 1〜70重量％であることを特徴とする請求項 1〜7のいずれかに榭脂組成物[8] The content of the component derived from the block (b) in the room temperature black mouth form insoluble component of the greave composition is 0.1 to 70% by weight, Nylon composition
(C)。 (C).
[9] 前記ォレフィン系ブロックポリマー (A2)は、ブロック (b)がブロック（a)—分子鎖当た り 0. 5〜5個結合していることを特徴とする請求項 1〜8のいずれかに記載の榭脂組 成物（C)。  [9] The olefin-based block polymer (A2) according to any one of claims 1 to 8, wherein 0.5 to 5 blocks (b) are bonded per block (a) -molecular chain. The rosin composition (C) according to crab.
[10] 請求項 1〜9の 、ずれかに記載の榭脂組成物（C)からなることを特徴とする接着剤  [10] An adhesive comprising the resin composition (C) according to any one of claims 1 to 9.
[11] 請求項 1〜9のいずれかに記載の榭脂組成物（C)からなることを特徴とするフィルム 又はシート。 [11] A film or sheet comprising the resin composition (C) according to any one of claims 1 to 9.
[12] 請求項 1〜9のいずれかに記載の榭脂組成物（C)からなることを特徴とする建材 · 土木用材料。  [12] A building material / civil engineering material comprising the resin composition (C) according to any one of claims 1 to 9.
[13] 請求項 1〜9のいずれかに記載の榭脂組成物（C)からなることを特徴とする自動車 内外装材又はガソリンタンク。  [13] An automobile interior / exterior material or a gasoline tank comprising the resin composition (C) according to any one of claims 1 to 9.
[14] 請求項 1〜9のいずれかに記載の榭脂組成物（C)からなることを特徴とする電気 · 電子部品。 [14] An electrical / electronic component comprising the resin composition (C) according to any one of claims 1 to 9.
[15] 請求項 1〜9のいずれか〖こ記載の榭脂組成物（C)を含むことを特徴とする水性エマ ノレジョン。  [15] An aqueous emulsion containing the rosin composition (C) according to any one of claims 1 to 9.
[16] 請求項 1〜9のいずれかに記載の榭脂組成物 (C)を含むことを特徴とする溶剤分 散体。  [16] A solvent dispersion comprising the resin composition (C) according to any one of claims 1 to 9.
[17] 請求項 1〜9のいずれかに記載の榭脂組成物（C)からなることを特徴とする医療 · 衛生用材料。  [17] A medical / sanitary material comprising the rosin composition (C) according to any one of claims 1 to 9.
[18] 請求項 1〜9のいずれかに記載の榭脂組成物（C)からなることを特徴とする日常雑 貨類。 [18] A daily miscellaneous product comprising the rosin composition (C) according to any one of claims 1 to 9. Coins.
[19] 請求項 1〜9のいずれかに記載の榭脂組成物（C)からなる層を少なくても 1層含む ことを特徴とする積層構造体。  [19] A laminated structure comprising at least one layer composed of the resin composition (C) according to any one of [1] to [9].
[20] ォレフィン系重合体を主要な構成成分として含む層（L1)、 [20] Layer (L1) containing an olefin polymer as a main constituent,
請求項 1〜9のヽずれかに記載の榭脂組成物 (C)を含む層（L2)、  A layer (L2) comprising the resin composition (C) according to any one of claims 1 to 9,
極性ビュル系プラスチック、芳香族ビニル系重合体、ポリエステル、ポリアミド、ポリ カーボネート、エンジニアリングプラスチック、生物由来ポリマー、熱可塑性エラストマ 一、天然製または人工繊維、および金属カゝら選ばれる少なくても 1種カゝらなる層（L3) 力 層（L1)Z層（L2)Z層（L3)の順に積層している構造を少なくても一部に有する ことを特徴とする請求項 19に記載の積層構造体。  Polar bull plastic, aromatic vinyl polymer, polyester, polyamide, polycarbonate, engineering plastic, bio-derived polymer, thermoplastic elastomer, natural or man-made fiber, and metal at least one kind selected 20. The laminated structure according to claim 19, wherein the layered structure (L3), the force layer (L1), the Z layer (L2), and the Z layer (L3) are laminated at least in part. body.
[21] 榭脂組成物（C)力 ポリオレフイン (A1)と、ォレフィン系ブロックポリマー (A2)とか ら構成されることを特徴とする請求項 20に記載の積層構造体。 21. The laminated structure according to claim 20, wherein the resin composition (C) is composed of polyolefin (A1) and olefin-based block polymer (A2).
[22] 榭脂組成物（C)を構成するォレフイン系ブロックポリマー (A2)を構成するブロック（ b)の示差走査型熱量計 (DSC)で測定したガラス転移温度 (Tg)が 25°C以下である ことを特徴とする請求項 21に記載の積層構造体。 [22] Glass transition temperature (Tg) measured by differential scanning calorimeter (DSC) of block (b) constituting olefin block polymer (A2) constituting rosin composition (C) is 25 ° C or less The laminated structure according to claim 21, wherein
[23] 榭脂組成物（C)を構成するォレフイン系ブロックポリマー (A2)を構成するブロック（ a)の DSCで測定した融点 (Tm)に起因する吸熱ピークが 50°C以上である結晶性ポ リオレフイン残基であることを特徴とする請求項 21または 22に記載の積層構造体。 [23] Crystallinity with an endothermic peak due to the melting point (Tm) measured by DSC of the block (a) constituting the olefin block polymer (A2) constituting the resin composition (C) of 50 ° C or higher 23. The laminated structure according to claim 21, wherein the laminated structure is a polyolefin residue.
PCT/JP2007/056573 2006-03-29 2007-03-28 Resin composition containing olefin block polymer and use of the same WO2007114134A1 (en)

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Applications Claiming Priority (10)

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JP2006092164A JP2007262325A (en) 2006-03-29 2006-03-29 Polymer blend comprising olefinic block polymer
JP2006-092164 2006-03-29
JP2006146751 2006-05-26
JP2006-146751 2006-05-26
JP2006-151401 2006-05-31
JP2006151400A JP2007321025A (en) 2006-05-31 2006-05-31 Polymer blend containing olefin-based block polymer
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